CN115954273B - Gas-phase iodine doped metal oxide thin film transistor and preparation method thereof - Google Patents
Gas-phase iodine doped metal oxide thin film transistor and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a gas-phase iodine-doped metal oxide thin film transistor and a preparation method thereof, which belong to the technical field of semiconductor materials and devices, wherein the transistor sequentially comprises a substrate, a dielectric layer, an active layer and a metal electrode from bottom to top, iodine ions are doped in the active layer, the substrate adopts any one of common glass, a silicon wafer and conductive glass, the metal electrode adopts any one of Al, ag, au, W, ta, pt, and the active layer is a nano-structured metal oxide material. The iodine-based post-treatment doping technology can control the electrical property of the material by controlling the exposure time of the metal oxide film and the thin film transistor in the sealing device filled with iodine vapor, is simpler and easier to realize than the existing doping technology in the material composition or film forming process, and has great significance for the research of new-generation thin film transistors.
Description
Technical Field
The invention belongs to the technical field of semiconductor materials and devices, and particularly relates to a gas-phase iodine-doped metal oxide thin film transistor and a preparation method thereof.
Background
Metal oxide semiconductors have been used as active channel materials in thin film transistors due to their excellent charge carrier mobility, high optical transmittance in the visible range, excellent chemical stability, and versatility in processing. Such as zinc oxide, indium zinc oxide, and indium gallium zinc oxide, have been widely studied and used. And metal oxide semiconductor-based thin film transistors have been used in various electronic applications such as electronic memory devices, chemical sensors, and active matrix displays. In order to realize the diversified applications thereof in the new generation electronic device industry, development of a technology capable of controlling the electrical properties of substances is urgently required. For this reason, studies on the influence of the composition ratio, the post-photodecomposition treatment, the dopant technology, and the like in materials composed of binary, ternary, and quaternary components have been attracting attention.
The doping technique can control and adjust the electrical characteristics of the oxide semiconductor material, and can overcome the dependence on the material. Currently, among studies of non-metal ion doped metal oxide semiconductors, the study of iodine doping is the most widespread. And in the iodine doping research of metal oxide semiconductors based on solution process, iodic acid is mostly used as a dopant, and is mixed with a metal oxide precursor solution in the early stage. After the iodine doping of the metal oxide semiconductor material based on the solution process is finished, a high-temperature sintering process is generally required, and due to the characteristic of easy sublimation of iodine, the iodine doped metal oxide film is greatly influenced by temperature in the sintering process, and the higher the sintering temperature is, the lower the iodine content is, so that the iodine doping amount cannot be accurately controlled. Based on the method, the invention provides an iodine doping post-treatment method, which does not need to mix with a metal oxide precursor solution in the early stage, is not influenced by the sintering temperature of a metal oxide material, and can accurately control the doping amount of iodine only by controlling the doping time in the later stage.
Disclosure of Invention
In order to solve the defects of the prior art and to distinguish the doping modes which are widely studied at present in the material composition and film forming process, the invention provides a gas-phase iodine doped metal oxide thin film transistor and a preparation method thereof.
The technical scheme of the invention provides a gas-phase iodine-doped metal oxide thin film transistor which sequentially comprises a substrate, a dielectric layer, an active layer and a metal electrode from bottom to top, wherein iodine ions are doped in the active layer.
Further, the substrate is any one of common glass, a silicon wafer and conductive glass, the metal electrode is any one of Al, ag, au, W, ta, pt, and the active layer is a metal oxide material with a nano structure.
Further, the dielectric layer, the active layer and the metal electrode are prepared by any one of a solution method, a vacuum deposition method and a magnetron sputtering method.
The technical scheme of the invention provides a preparation method of a gas-phase iodine-doped metal oxide thin film transistor, which adopts the metal oxide thin film transistor and comprises the following steps:
step 2: respectively carrying out ultrasonic cleaning treatment on the P-type silicon substrate by adopting acetone, isopropanol and deionized water, drying by adopting nitrogen, and finally carrying out secondary cleaning treatment on the silicon nitride surface by adopting a plasma cleaning machine to obtain the high-hydrophilicity clean silicon nitride surface;
step 3: coating an indium oxide precursor solution on the surface of silicon nitride by adopting a spin coating mode to obtain a metal oxide active layer, wherein the metal oxide active layer is of an amorphous microcrystalline structure, and the root mean square roughness is 0.240-0.248 nanometers;
step 4: the metal oxide active layer obtained by spin coating is placed in an atmospheric environment for preliminary low-temperature pre-baking, then placed in a muffle furnace for high-temperature annealing at 100-400 ℃ to obtain a metal oxide film, namely an indium oxide film, and physical property characterization is carried out;
step 5: depositing an aluminum film on the surface of the metal oxide film subjected to physical property characterization in a vacuum deposition mode to form a metal electrode, thereby obtaining a metal oxide thin film transistor;
step 6: and inverting the metal oxide thin film transistor subjected to electrical property measurement on the top of the sealing device filled with iodine vapor, and carrying out iodine doping.
Further, the thickness of the metal electrode is 10-200 nanometers, and the thickness of the metal oxide film is 20-100 nanometers.
Further, by controlling the time of the metal oxide thin film transistor in the sealing device filled with iodine vapor, the doping amount of iodine is controlled, thereby controlling the electrical performance of the transistor.
Further, the iodine doping time is 0-10 seconds.
The beneficial technical effects are as follows:
the invention provides a method for doping iodine on a solution process type metal oxide semiconductor in a gas phase mode based on the special properties of easy sublimation and good physical and chemical stability of iodine, which breaks through the traditional doping process mode, overcomes the dependence of the current semiconductor material and is not limited by the temperature of high-temperature sintering. The doping amount of iodine can be controlled by controlling the exposure time of the metal oxide thin film transistor in iodine vapor, so that the purpose of adjusting the electrical property of the material is achieved, and the method has important significance for researching new generation thin film transistors.
Drawings
Fig. 1 is a schematic diagram of a vapor phase iodine doped metal oxide thin film transistor according to the present invention.
Wherein, 100-substrate; 101-a dielectric layer; 102-an active layer; 103-metal electrode.
Fig. 2 is an XPS diagram of the metal oxide thin film prepared in comparative example 1.
Fig. 3 is an XPS diagram of the metal oxide thin film prepared in example 1.
Fig. 4 is an XPS diagram of the metal oxide thin film prepared in example 2.
Fig. 5 is an output characteristic curve of the metal oxide thin film transistor prepared in comparative example 1.
Fig. 6 is an output characteristic curve of the metal oxide thin film transistor prepared in example 1.
Fig. 7 is an output characteristic curve of the metal oxide thin film transistor prepared in comparative example 2.
Fig. 8 is an output characteristic curve of the metal oxide thin film transistor prepared in example 2.
Fig. 9 is a transfer characteristic curve of the metal oxide thin film transistor prepared in comparative example 1.
Fig. 10 is a transfer characteristic curve of the metal oxide thin film transistor prepared in example 1.
Fig. 11 is a transfer characteristic curve of the metal oxide thin film transistor prepared in comparative example 2.
Fig. 12 is a transfer characteristic curve of the metal oxide thin film transistor prepared in example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail with reference to the accompanying drawings and examples. The examples described below are by way of example only and are not to be construed as limiting the invention. It should be understood that in the description of the present invention, references to orientations or positional relationships as indicated in the top, bottom, upper, lower, left, right, etc. are based on the orientations or positional relationships shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the device or element being referred to must have a specific orientation, be configured and operated in a specific orientation, and therefore should not be construed as limiting the present invention.
In order to further illustrate the technical solution of the present invention, a detailed description will be given below with reference to a plurality of specific embodiments.
Example 1:
as shown in fig. 1, the gas-phase iodine-doped metal oxide thin film transistor sequentially comprises a substrate 100, a dielectric layer 101, an active layer 102 and a metal electrode 103 from bottom to top, wherein the dielectric layer 101 is made of silicon nitride, and iodine ions are doped in the active layer 102.
The preparation method of the gas-phase iodine doped metal oxide thin film transistor comprises the following steps:
step 2: respectively carrying out ultrasonic cleaning treatment on the P-type silicon substrate for 15 minutes and 30 minutes by adopting acetone and isopropanol, cleaning the isopropanol remained on the surface by using deionized water to ensure that the silicon nitride surface is clean and free of organic substances, drying after drying by adopting nitrogen, removing the residual moisture and oxidative or reductive gas on the silicon nitride surface, and finally carrying out secondary cleaning treatment on the silicon nitride surface by adopting a plasma cleaning machine to obtain the high-hydrophilicity clean silicon nitride surface;
step 3: placing a clean substrate in a spin coater, spin-coating an indium oxide precursor solution at 5000 rpm for 35 seconds, and coating the indium oxide precursor solution on the surface of silicon nitride to obtain a metal oxide active layer, wherein the metal oxide active layer is of an amorphous microcrystalline structure, and the root mean square roughness is 0.240-0.248 nanometers;
step 4: pre-baking the metal oxide active layer obtained by spin coating at 80 ℃ for 5 minutes in a hot table, then annealing at 300 ℃ in a muffle furnace for 60 minutes to obtain a metal oxide film, namely an indium oxide film, and carrying out physical property characterization;
step 5: depositing an aluminum film on the surface of the metal oxide film subjected to physical property characterization to form a metal electrode, so as to obtain a metal oxide thin film transistor 1, wherein the length L=80 micrometers and the width W=2000 micrometers of a conductive channel of the metal electrode;
step 6: the metal oxide thin film transistor subjected to electrical property measurement is inverted to the top of a sealing device filled with iodine vapor, and 5 seconds of doping post-treatment is performed to obtain a metal oxide thin film transistor 2.
Comparative example 1:
comparative example 1 is a metal oxide thin film transistor 1 obtained in example 1 without step 6.
Example 2:
as shown in fig. 1, the gas-phase iodine-doped metal oxide thin film transistor sequentially comprises a substrate 100, a dielectric layer 101, an active layer 102 and a metal electrode 103 from bottom to top, wherein the dielectric layer 101 is made of silicon nitride, and iodine ions are doped in the active layer 102.
The preparation method of the gas-phase iodine doped metal oxide thin film transistor comprises the following steps:
step 2: respectively carrying out ultrasonic cleaning treatment on the P-type silicon substrate for 15 minutes and 30 minutes by adopting acetone and isopropanol, cleaning the isopropanol remained on the surface by using deionized water to ensure that the silicon nitride surface is clean and free of organic substances, drying after drying by adopting nitrogen, removing the residual moisture and oxidative or reductive gas on the silicon nitride surface, and finally carrying out secondary cleaning treatment on the silicon nitride surface by adopting a plasma cleaning machine to obtain the high-hydrophilicity clean silicon nitride surface;
step 3: placing a clean substrate in a spin coater, spin-coating an indium oxide precursor solution at 5000 rpm for 35s on the surface of silicon nitride to obtain a metal oxide active layer, wherein the metal oxide active layer is of an amorphous microcrystalline structure, and the root mean square roughness is 0.240-0.248 nanometers;
step 4: pre-baking the metal oxide active layer obtained by spin coating at 80 ℃ for 5 minutes in a hot table, then annealing at 300 ℃ in a muffle furnace for 60 minutes to obtain a metal oxide film, namely an indium oxide film, and carrying out physical property characterization;
step 5: depositing an aluminum film on the surface of the metal oxide film subjected to physical property characterization to form a metal electrode, so as to obtain a metal oxide thin film transistor 3, wherein the length L=80 micrometers and the width W=2000 micrometers of a metal electrode conducting channel;
step 6: the metal oxide thin film transistor after electrical property measurement was inverted on top of the sealing device filled with iodine vapor, and subjected to doping post-treatment for 10 seconds to obtain a metal oxide thin film transistor 4.
Comparative example 2:
comparative example 2 is the metal oxide thin film transistor 3 obtained in example 2 without going through step 6.
To better illustrate the properties of the resulting materials and transistors, the materials and transistors of examples 1 and 2 and comparative examples 1 and 2 were subjected to corresponding performance tests:
as shown in fig. 2 to 4, the chemical structure and composition of the metal oxide thin films of comparative example 1 and examples 1 and 2 were studied by X-ray photoelectron spectroscopy (XPS), and the chemical structure and composition of the metal oxide thin film of comparative example 2 were substantially the same as those of comparative example 1. According to the change of the peak of oxygen element O1s in the metal oxide film in the figure, the oxygen vacancy (O II ) And metal hydroxide (O) III ) The relative peak area of the related sub-peaks is reduced, which shows that the method for carrying out iodine doping on the metal oxide film can effectively control the oxygen vacancy content in the metal oxide material, and can enable more iodine ions to be doped into the film along with the extension of the exposure time of the metal oxide film transistor in iodine vapor, thereby playing a role in reducing the concentration of electron carriers.
Fig. 5 to 6 are output characteristics of the thin film transistors of comparative example 1 and example 1, respectively, wherein the output characteristics of the thin film transistor of example 1 are substantially the same due to the small drain current when the gate voltages are 0V and 5V as shown in fig. 6; fig. 7 to 8 are output characteristics of the thin film transistors of comparative example 1 and example 2, respectively, wherein the output characteristics of the thin film transistor of example 2 are substantially the same due to the small drain current when the gate voltages are 0V and 5V as shown in fig. 8; FIGS. 9 to 10 are transfer characteristic curves of the thin film transistors of comparative example 1 and example 1, respectively; fig. 11 to 12 are transfer characteristic curves of the thin film transistors in comparative example 1 and example 2, respectively. The result shows that the doping of iodine can reduce the drain current of the metal oxide thin film transistor, reduce the electron mobility and generate rightward shift of the grid voltage; and the greater the variation in electrical properties of the metal oxide thin film transistor with the extension of the doping time.
It should be understood that the above description is not intended to limit the invention to the particular embodiments disclosed, but to limit the invention to the particular embodiments disclosed, and that the invention is not limited to the particular embodiments disclosed, but is intended to cover modifications, adaptations, additions and alternatives falling within the spirit and scope of the invention.
Claims (5)
1. The preparation method of the gas-phase iodine-doped metal oxide thin film transistor sequentially comprises a substrate, a dielectric layer, an active layer and a metal electrode from bottom to top, wherein iodine ions are doped in the active layer;
the preparation method is characterized by comprising the following steps:
step 1; preparing a precursor solution containing indium ions and a P-type silicon substrate with a silicon nitride dielectric layer;
step 2: respectively carrying out ultrasonic cleaning treatment on the P-type silicon substrate by adopting acetone, isopropanol and deionized water, drying by adopting nitrogen, and finally carrying out secondary cleaning treatment on the silicon nitride surface by adopting a plasma cleaning machine to obtain the high-hydrophilicity clean silicon nitride surface;
step 3: coating an indium oxide precursor solution on the surface of silicon nitride by adopting a spin coating mode to obtain a metal oxide active layer, wherein the metal oxide active layer is of an amorphous microcrystalline structure, and the root mean square roughness is 0.240-0.248 nanometers;
step 4: the metal oxide active layer obtained by spin coating is placed in an atmospheric environment for preliminary low-temperature pre-baking, and then placed in a muffle furnace for high-temperature annealing at 100-400 ℃ to obtain a metal oxide film, namely an indium oxide film;
step 5: depositing an aluminum film on the surface of the metal oxide film subjected to physical property characterization in a vacuum deposition mode to form a metal electrode, thereby obtaining a metal oxide thin film transistor;
step 6: inverting the metal oxide thin film transistor subjected to electrical property measurement to the top of a sealing device filled with iodine vapor for iodine doping;
the electrical performance of the transistor is controlled by controlling the time of the metal oxide thin film transistor in the sealing device filled with iodine vapor and controlling the doping amount of iodine.
2. The method for preparing a vapor phase iodine doped metal oxide thin film transistor according to claim 1, wherein the substrate is any one of common glass, a silicon wafer and conductive glass, the metal electrode is any one of Al, ag, au, W, ta, pt, and the active layer is a nano-structured metal oxide material.
3. The method for preparing a vapor phase iodine doped metal oxide thin film transistor according to claim 1, wherein the dielectric layer, the active layer and the metal electrode are prepared by any one of a solution method, a vacuum deposition method and a magnetron sputtering method.
4. The method for manufacturing a vapor phase iodine doped metal oxide thin film transistor according to claim 1, wherein the thickness of the metal electrode is 10-200 nm, and the thickness of the metal oxide thin film is 20-100 nm.
5. The method for preparing a vapor phase iodine doped metal oxide thin film transistor according to claim 1, wherein the iodine doping time is 0-10 seconds.
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| WO2009065180A1 (en) * | 2007-11-23 | 2009-05-28 | The University Of Queensland | Non-metal doped metal oxide nanosheets and method of production thereof |
| CN103311128A (en) * | 2013-06-13 | 2013-09-18 | 北京大学深圳研究生院 | Self-aligning metal oxide thin film transistor and manufacturing method thereof |
| CN113539801A (en) * | 2021-06-23 | 2021-10-22 | 华南理工大学 | Metal oxide nitrogen doping method and metal oxide thin film transistor |
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| KR20160137843A (en) * | 2015-05-22 | 2016-12-01 | 엘지디스플레이 주식회사 | Thin Film Transistor Substrate Having High Reliability Metal Oxide Semiconductor Material |
| CN105355793B (en) * | 2015-11-06 | 2018-05-29 | 昆明物理研究所 | A kind of organic detectors of the photovoltaic type of the OPV I2 dopings of near-infrared visible ray |
| CN105460930B (en) * | 2016-01-04 | 2017-05-31 | 河南工程学院 | A kind of regulation and control and the method and device of sign Graphene band gap |
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| CN110718468B (en) * | 2019-09-26 | 2022-08-02 | 深圳大学 | Samarium-doped metal oxide thin film transistor and preparation method and application thereof |
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| WO2009065180A1 (en) * | 2007-11-23 | 2009-05-28 | The University Of Queensland | Non-metal doped metal oxide nanosheets and method of production thereof |
| CN103311128A (en) * | 2013-06-13 | 2013-09-18 | 北京大学深圳研究生院 | Self-aligning metal oxide thin film transistor and manufacturing method thereof |
| CN113539801A (en) * | 2021-06-23 | 2021-10-22 | 华南理工大学 | Metal oxide nitrogen doping method and metal oxide thin film transistor |
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