CN111628017A - Hydrogen-doped indium gallium zinc oxide film layer, preparation method and application thereof, transistor and preparation method thereof - Google Patents
Hydrogen-doped indium gallium zinc oxide film layer, preparation method and application thereof, transistor and preparation method thereof Download PDFInfo
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 136
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- 229910052733 gallium Inorganic materials 0.000 title claims abstract description 64
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- 238000002360 preparation method Methods 0.000 title claims abstract description 24
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- JBRZTFJDHDCESZ-UHFFFAOYSA-N AsGa Chemical compound [As]#[Ga] JBRZTFJDHDCESZ-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 229910000661 Mercury cadmium telluride Inorganic materials 0.000 description 1
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Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
- H01L31/0321—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 characterised by the doping material
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- H01L31/10—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors characterised by potential barriers, e.g. phototransistors
- H01L31/101—Devices sensitive to infrared, visible or ultraviolet radiation
- H01L31/112—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor
- H01L31/113—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor being of the conductor-insulator-semiconductor type, e.g. metal-insulator-semiconductor field-effect transistor
- H01L31/1136—Devices sensitive to infrared, visible or ultraviolet radiation characterised by field-effect operation, e.g. junction field-effect phototransistor being of the conductor-insulator-semiconductor type, e.g. metal-insulator-semiconductor field-effect transistor the device being a metal-insulator-semiconductor field-effect transistor
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Abstract
The invention discloses a hydrogen-doped indium gallium zinc oxide film layer, a preparation method and application thereof, a transistor and a preparation method thereof. The hydrogen-doped indium gallium zinc oxide film layer is applied to the photoelectric transistor, the actual requirements of the visible light detection field on the indium gallium zinc oxide type photoelectric transistor can be met, and the photoelectric transistor plays an important role in the fields of display and imaging, optical communication, remote sensing, biological medical treatment and the like.
Description
Technical Field
The invention relates to the technical field of semiconductor material preparation and photoelectric device, in particular to a hydrogen-doped indium gallium zinc oxide film layer, a preparation method and application thereof, a transistor and a preparation method thereof.
Background
With the advance of artificial intelligence and automation, the realization of automatic identification and calculation becomes the pursuit target of the new generation of science and technology development, and the detection technology of visible light is a task to be solved firstly. The detection of visible light is based on the premise of simulating human eye function, and the identification and resolution capability of the target is improved on the basis. Therefore, visible light detection plays an important role in the fields of display and imaging, optical communication, remote sensing, biomedical treatment, and the like.
The traditional material for visible light detection is mainly a crystalline silicon material, and in the course of years of industrial use improvement, the silicon-based visible light detection material has been produced in large scale and has the characteristics of low cost, mature process and high visible light resolution, but the silicon-based material cannot meet the process requirements of multiple aspects such as flexible bending. In the meantime, there are also a number of new detection materials emerging, such as mercury cadmium telluride materials, gallium arsenic based compound materials, organic polymer materials, etc., but considering the environmental protection and cost of the materials and the complexity of the process, new material and process fields still need to be developed.
IGZO has received much attention in the research of detectors as a promising light absorbing material under the stream of advocating green environmental protection. However, IGZO materials have a low response in the visible light range, and further research on the materials is needed to better meet the requirements of the field of detection of visible light.
Disclosure of Invention
In order to solve the problems that an IGZO light absorption material in the existing phototransistor has low response in a visible light range and cannot be well applied to the field of visible light detection, the invention provides a novel IGZO material and a preparation method thereof, and further provides a transistor based on the novel IGZO material and a preparation method thereof, wherein the transistor can be used for visible light detection.
In order to achieve the above object, the present invention provides a method for preparing a hydrogen-doped indium gallium zinc oxide film, comprising: preparing a hydrogen-doped indium gallium zinc oxide film layer by adopting a film coating process in a first gas atmosphere; the first gas atmosphere comprises hydrogen, and the band gap width of the hydrogen-doped indium gallium zinc oxide film layer is smaller than or equal to the photon energy of visible light.
Further, the first gas atmosphere also comprises inert gas, and the volume ratio of the hydrogen to the inert gas is less than or equal to 10: 90.
Further, the preparation method further comprises the following steps: and annealing the hydrogen-doped indium gallium zinc oxide film layer.
Further, the preparation method further comprises the following steps: the step of annealing the hydrogen-doped indium gallium zinc oxide film layer comprises the following steps: and annealing the hydrogen-doped indium gallium zinc oxide film layer in a mixed gas atmosphere, wherein the mixed gas comprises hydrogen and inert gas, and the volume ratio of the hydrogen to the inert gas is less than or equal to 10: 90.
The invention further provides the hydrogen-doped indium gallium zinc oxide film layer prepared by the preparation method.
The invention further provides the application of the hydrogen-doped indium gallium zinc oxide film layer in a semiconductor device.
The invention further provides a manufacturing method of the transistor, which comprises the steps of manufacturing a gate electrode layer, a gate dielectric layer, the hydrogen-doped indium gallium zinc oxide film layer, a channel layer, a source electrode and a drain electrode, wherein the method for manufacturing the hydrogen-doped indium gallium zinc oxide film layer is the method for manufacturing the hydrogen-doped indium gallium zinc oxide film layer.
Further, the method for manufacturing the gate electrode layer, the gate dielectric layer, the hydrogen-doped indium gallium zinc oxide film layer, the channel layer, the source electrode and the drain electrode comprises the following steps:
manufacturing and forming the gate electrode layer on a substrate;
manufacturing and forming the gate dielectric layer on the gate electrode layer;
forming the hydrogen-doped indium gallium zinc oxide film layer on the gate dielectric layer by adopting the preparation method of the hydrogen-doped indium gallium zinc oxide film layer;
manufacturing and forming the channel layer on the hydrogen-doped indium gallium zinc oxide film layer;
and manufacturing and forming the source electrode and the drain electrode which are spaced from each other on the channel layer.
The invention further provides a transistor manufactured by the manufacturing method of the transistor.
The present invention also provides a transistor, comprising: gate electrode layer, gate dielectric layer, channel layer, source electrode and drain electrode, characterized in that, the transistor still includes: and a light absorbing layer disposed above or below at least one of the gate electrode layer, the gate dielectric layer, the channel layer, the source electrode, and the drain electrode, wherein a band gap width of the light absorbing layer is less than or equal to a photon energy of visible light.
In the transistor, the gate electrode layer is provided over a substrate;
the gate dielectric layer is arranged on the gate electrode layer;
the light absorption layer is arranged on the gate dielectric layer;
the channel layer is disposed on the light absorbing layer;
the source electrode and the drain electrode are disposed on the channel layer, and the source electrode and the drain electrode are spaced apart from each other.
Further, the light absorption layer is a hydrogen-doped indium gallium zinc oxide film layer, wherein the hydrogen-doped indium gallium zinc oxide film layer is prepared by the preparation method of the hydrogen-doped indium gallium zinc oxide film layer.
Compared with the prior art, the invention has the following beneficial effects:
compared with the common indium gallium zinc oxide which does not basically respond to visible light, the band gap of the indium gallium zinc oxide film layer doped with hydrogen provided by the invention is less than or equal to the photon energy of the visible light, so that photons of the visible light can be absorbed and electrons can be generated, and photocurrent can be formed under the action of an external electric field.
The transistor provided by the invention uses the hydrogen-doped indium gallium zinc oxide film layer as the light absorption layer, so that the light absorption layer can absorb photons of visible light and generate electrons, and under the action of an external electric field, a photocurrent is formed. Therefore, the manufactured transistor can generate good response to visible light and can detect in a visible light wave band.
Drawings
The above and other aspects, features and advantages of embodiments of the present invention will become more apparent from the following description taken in conjunction with the accompanying drawings, in which:
FIG. 1 is a schematic diagram of a phototransistor according to the present invention;
FIG. 2 is a current responsivity curve of the phototransistors of example 1 of the present invention and comparative example 1;
FIG. 3 is a transfer characteristic curve of a phototransistor used in embodiment 1 of the present invention;
fig. 4 is a transfer characteristic curve of the phototransistor of comparative example 1 of the present invention.
Detailed Description
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the specific embodiments set forth herein. Rather, these embodiments are provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
Based on the problems that an IGZO light absorption material in the existing phototransistor has low response in a visible light range and cannot be well applied to the field of visible light detection, the invention provides a novel IGZO material and a preparation method thereof, and further provides a transistor based on the novel IGZO material and a preparation method thereof, wherein the transistor can be used for visible light detection.
1. Some embodiments of the present invention provide a method for preparing a novel IGZO film layer, including: introducing hydrogen in the preparation process of the indium gallium zinc oxide film layer to form a hydrogen-doped indium gallium zinc oxide film layer, wherein the band gap width of the hydrogen-doped indium gallium zinc oxide is less than or equal to the photon energy of visible light.
In some embodiments, the method for preparing the hydrogen-doped indium gallium zinc oxide film layer by using the magnetron sputtering technology comprises the following steps:
taking indium-gallium-zinc oxide with the atomic ratio of indium to gallium to zinc to oxygen of 1:1:1:4 as a target material, and placing a carrier in a magnetron sputtering reaction cavity;
evacuating the gas in the reaction chamber until its internal pressure reaches 5 × 10-5Pa below;
introducing a first mixed gas into the magnetron sputtering reaction cavity, wherein the first mixed gas comprises hydrogen and inert gas, and the volume ratio of the hydrogen to the inert gas is controlled to be less than or equal to 10:90 by taking the total volume of the hydrogen and the inert gas as 100 parts;
after sputtering glow is regulated and controlled, the working pressure and power of the magnetron sputtering reaction cavity are set, and then the hydrogen-doped indium gallium zinc oxide is sputtered and deposited.
In other embodiments, the method further comprises annealing the hydrogen-doped indium gallium zinc oxide film layer in a tubular annealing furnace, wherein the annealing process comprises the following process parameters: the annealing atmosphere contains inert gas, the annealing temperature is 50-150 ℃, and the internal pressure of the annealing furnace is 10Pa-10 kPa.
Wherein whether hydrogen is added to the annealing atmosphere is determined according to whether the IGZO material has the expected visible light absorption performance. When hydrogen is added to the annealing atmosphere, the volume ratio of the hydrogen to the inert gas is controlled to be less than or equal to 10:90 based on 100 parts by volume of the total of the hydrogen and the inert gas.
At itIn other embodiments, the hydrogen-doped InGaZn oxide film layer is prepared by a chemical vapor deposition process, specifically, In an atmosphere containing hydrogen gas2O3、Ga2O3And depositing and growing a hydrogen-doped indium gallium zinc oxide film layer by taking ZnO as a target material.
2. Some embodiments of the present invention further provide a hydrogen-doped indium gallium zinc oxide film layer prepared based on the above preparation method.
Wherein the atomic ratio of indium, gallium, zinc and oxygen of the hydrogen-doped indium gallium zinc oxide is the same as that of the target material and is 1:1:1: 4.
The structure of the IGZO material doped with hydrogen is an amorphous structure, wherein the doping of hydrogen atoms enables the material to have deep-level defects, and the band gap of the material is less than or equal to the photon energy of visible light; in3+The ions can form a 5S electron orbit, which is beneficial to the transmission of high-speed free carriers in the semiconductor; gallium oxide (Ga)2O3) Has stable metal-oxygen ion bonds, which can inhibit the generation of oxygen vacancies in the material; zinc ions in zinc oxide (ZnO) can form a stable tetrahedral structure.
3. Some embodiments of the present invention further provide a use of the above-mentioned hydrogen-doped indium gallium zinc oxide: and applying the hydrogen-doped indium gallium zinc oxide film layer as a semiconductor material layer in a semiconductor device.
The hydrogen-doped indium gallium zinc oxide film layer has a good visible light response effect, because the band gap of the hydrogen-doped indium gallium zinc oxide film layer is less than or equal to the photon energy of visible light, photons of the visible light can be absorbed and electrons can be generated, and a photocurrent is formed under the action of an external electric field.
4. Some embodiments of the present invention further provide a method for manufacturing a phototransistor, which includes the steps of manufacturing a gate electrode layer, a gate dielectric layer, a light absorbing layer, a channel layer, a source electrode, and a drain electrode, where the light absorbing layer is a hydrogen-doped indium gallium zinc oxide film layer, and the method for manufacturing the light absorbing layer is the method for manufacturing the hydrogen-doped indium gallium zinc oxide film layer.
The phototransistor includes a bottom gate structure phototransistor and a top gate structure phototransistor.
The bottom gate structure further comprises a bottom gate-top contact structure and a bottom gate-bottom contact structure. In the bottom gate-top contact structure, a substrate, a gate electrode layer, a gate dielectric layer, a light absorption layer, a channel layer, a source electrode and a drain electrode are sequentially arranged from bottom to top, and the source electrode and the drain electrode are far away from the substrate. The area of the light absorption layer influenced by the electric field of the gate electrode layer in the structure is larger than that of a device structure with the source electrode and the drain electrode at the bottom, so that the structure has high carrier mobility. In the bottom gate-bottom contact structure, a substrate, a gate electrode layer, a gate dielectric layer, a source electrode and a drain electrode which are arranged at intervals on the same layer, a channel layer and a light absorption layer are sequentially arranged from bottom to top.
The top gate structure type photoelectric transistor is sequentially provided with a substrate, a light absorption layer, a channel layer, a source electrode, a drain electrode, a gate dielectric layer and a gate electrode layer from bottom to top, wherein the source electrode and the drain electrode are arranged at intervals on the same layer.
Some embodiments of the present invention provide a method of fabricating a phototransistor having a bottom-gate-top contact structure, comprising the steps of:
(1) the substrate of the phototransistor is selected.
(2) A gate electrode layer is formed over the substrate.
(3) And forming a gate dielectric layer on the gate electrode layer.
(4) And forming a light absorption layer on the gate dielectric layer, wherein the material of the light absorption layer comprises IGZO doped with hydrogen.
(5) A channel layer is formed on the light absorbing layer.
(6) Forming a source electrode and a drain electrode on the channel layer.
With respect to step (1), in some preferred embodiments, the substrate may be selected from any one of a silicon substrate, a silicon oxide substrate, a glass substrate, a ceramic substrate, and a flexible polymer substrate. The flexible polymer substrate may be a polyethylene terephthalate (PET) substrate, a polyethylene naphthalate (PEN) substrate, or a Polyimide (PI) substrate.
For step (2), in some preferred embodiments, the material of the gate electrode layer may be selected from any one of metal molybdenum, metal aluminum, indium tin oxide, and aluminum-doped zinc oxide.
With respect to step (2), in some preferred embodiments, a magnetron sputtering technique is used to form the gate electrode layer, specifically: and (3) putting the cleaned silicon wafer substrate into a magnetron sputtering reaction cavity, and growing a molybdenum (Mo) electrode layer with the thickness of 1 micrometer by direct current sputtering. In order to improve adhesion and conductivity, when the Mo electrode layer is grown, it may be grown in two steps: firstly, growing a loose Mo electrode layer under high pressure (2.8Pa, sputtering for 19 circles under 350W power) to improve the adhesion with a substrate; and secondly, growing the Mo electrode layer of the dense layer under low pressure (0.3Pa air pressure and 9 turns of 1000W power sputtering) to optimize the conductivity of the Mo electrode layer.
For step (3), in some preferred embodiments, the material of the gate dielectric layer may be selected from aluminum oxide (Al)2O3) Silicon dioxide (SiO)2) Silicon nitride Si3N4Titanium dioxide (TiO)2) Any one of them.
With respect to step (3), in some preferred embodiments, a layer of Al with a thickness of 10-60nm is deposited on the gate electrode layer by Atomic Layer Deposition (ALD) at a temperature of room temperature-150 ℃2O3The film serves as a gate dielectric layer. Al (Al)2O3The mobility of the polymer can reach 8cm2/V-1s-1And the growth temperature is low, so that the flexible substrate is suitable for growth on the flexible substrate.
For step (3), in some preferred embodiments, the product of step (2) is placed in an ALD reaction chamber, evacuated to 5Pa, and introduced with an aluminum source for 300ms to deposit aluminum atoms on the electrode layer, evacuated for 3s to remove excess aluminum source, and introduced with N2Washing off the aluminum source in the cavity, pumping for 15s, introducing water vapor for 3s, providing an oxygen source, pumping for 3s, and introducing N2Pumping for 15s, washing off excessive oxygen source, repeating the cycle for 400 times, and sputtering to grow 40nm Al2O3And the growth temperature of the gate dielectric film is room temperature.
With respect to step (4), in the embodiment proposed by the present invention, the material of the light absorbing layer is hydrogen-doped indium gallium zinc oxide (abbreviated as IGZO for indium gallium zinc oxide). This is due to: the IGZO material not doped with hydrogen has a large band gap, absorbs only light having a short wavelength, and is almost completely optically transparent in the infrared and visible light regions. The doping of hydrogen causes the IGZO material to form deep-level defects, so that the band gap of the IGZO material is smaller than or equal to the photon energy of visible light, and therefore, the IGZO material can generate better response to the visible light. By adjusting the concentration of hydrogen doping, hydrogen-doped IGZO materials having different band gaps can be obtained.
In addition, the IGZO material belongs to an environment-friendly material, no harmful substances are generated in the preparation process, and the production environment is excellent.
For step (4), the thickness of the light absorbing layer is preferably 5-50 nm. The light absorbing layer may not be too thick to ensure that the generated carriers can diffuse into the channel layer as quickly as possible.
With respect to step (4), in some preferred embodiments, the fabrication technique of the light absorption layer may be selected from any one of magnetron sputtering, atomic layer deposition, vacuum evaporation, and electron beam coating.
In some embodiments, where magnetron sputtering is used to form the light absorbing layer, step (4) comprises:
(4-10): and placing the substrate with the gate electrode layer and the gate dielectric layer in a magnetron sputtering reaction cavity.
(4-11) evacuating the gas in the reaction chamber until its internal pressure reaches 5 × 10-5Pa or less.
(4-12): and introducing a first mixed gas containing hydrogen and inert gas into the magnetron sputtering reaction cavity.
(4-13): after sputtering glow is regulated and controlled, the working pressure of the magnetron sputtering reaction cavity is set to be 0.9Pa, and the power is 100W.
For the step (4-12), if the volume fraction of hydrogen is too small, the band gap of IGZO cannot reach the photon energy absorption level of visible light; when the volume fraction of hydrogen is too large, the IGZO may be excessively defective, which may affect the probing performance of the device. In some preferred embodiments, the volume ratio of hydrogen to inert gas in the first mixed gas is less than or equal to 10:90, based on 100 parts by volume of the total hydrogen and inert gas. In a further preferred embodiment, the volume ratio of hydrogen to inert gas is equal to 4: 96.
In order to further improve the performance of the device, annealing treatment can be carried out on the indium gallium zinc oxide film doped with hydrogen. The conditions of the annealing treatment include: the annealing temperature is set to 50-150 ℃, the annealing pressure is set to 10Pa-10kPa, and the gas environment is a second mixed gas, wherein the second mixed gas comprises hydrogen and inert gas. It should be noted that too high an annealing temperature may result in loss of components. In the second mixed gas, the volume ratio of the hydrogen to the inert gas is less than or equal to 10:90 based on 100 parts by volume of the total of the hydrogen and the inert gas. Specifically, the ratio of the hydrogen gas in the second mixed gas is determined according to whether the hydrogen-doped IGZO has the expected visible light absorption performance, and therefore, the ratio of the hydrogen gas in the second mixed gas to the hydrogen gas in the first mixed gas is not limited to the second mixed gas.
The inert gas in the embodiment of the present invention refers to a gas that does not affect the formation of the light absorbing layer, and is preferably nitrogen or a rare gas (such as helium, neon, or argon).
For step (4), In may also be employed In some embodiments of forming the light absorbing layer2O3、Ga2O3And depositing the hydrogen-doped indium gallium zinc oxide by using ZnO as a target material, and controlling the atomic ratio of In to Ga to Zn to O to be 1 to 4. By adjusting In2O3、Ga2O3The ZnO is used in a proportion to achieve the atomic ratio, for example: the ratio of the amounts of the substances is generally controlled to n (In)2O3):n(Ga2O3) N (zno) ═ x: x:2x, where n represents the amount of the substance and x is an arbitrary number.
With respect to step (5), the channel layer is an indispensable part of the transistor, and carriers generated by the light absorption layer due to photoresponse flow in the channel layer under the regulation of the source-drain voltage. The channel layer material may not be identical to the absorber layer material, but the mobility is required to be as high as possible. In some preferred embodiments, the material of the channel layer is selected from any one of indium gallium zinc oxide, hydrogen-doped indium gallium zinc oxide, amorphous silicon, graphene, and molybdenum disulfide.
The channel layer forming step includes: a thin film is grown on the light absorbing layer, and then a channel pattern is etched on the surface of the thin film. There are various etching methods, and the present invention does not specifically limit the etching process. Preferably, the channel layer thin film has a thickness of 10 to 150 nm.
For step (6), the source electrode is selected from a nickel electrode or an aluminum electrode; the drain electrode is selected from a nickel electrode or an aluminum electrode.
In some preferred embodiments, the Ni source electrode and the Ni drain electrode are manufactured by an evaporation method, and the specific steps comprise covering a sample with a mask plate, placing the sample into a chamber, and vacuumizing to 6 × 10-3And Pa, sequentially turning on a heating electric cabinet, cooling water, an electric fan and the sample to rotate, pressurizing and adjusting the electron beam current to 4/s, and evaporating the Ni film to be about 2 mu m thick.
In some preferred embodiments, the electrodes may also be formed on the channel layer by an electron beam evaporation method, in which the source electrode and the drain electrode are not in direct contact and are located at both sides of the channel layer.
5. Some embodiments of the present invention provide a phototransistor having a bottom gate-top contact structure formed according to the above-mentioned manufacturing method, and a schematic structural diagram thereof is shown in fig. 1. The photoelectric transistor is of a film layer structure and comprises a substrate 1, a gate electrode 2, a gate dielectric layer 3, a light absorption layer 4 and a channel layer 5 which are sequentially overlapped, wherein an active electrode 6 and a drain electrode 7 are arranged on two sides of the channel layer; wherein the material of the light absorption layer comprises IGZO doped with hydrogen.
The substrate 1 may be any one of a silicon substrate, a silicon oxide substrate, a glass substrate, a ceramic substrate, and a flexible polymer substrate. The flexible polymer substrate may be a polyethylene terephthalate (PET) substrate, a polyethylene naphthalate (PEN) substrate, or a Polyimide (PI) substrate.
The gate electrode 2 may be any one of a molybdenum electrode, an aluminum electrode, an indium tin oxide electrode, and an aluminum-doped zinc oxide electrode.
Wherein, the gate dielectric layer 3 may be aluminum oxide (Al)2O3) Silicon dioxide (SiO)2) Silicon nitride Si3N4Titanium dioxide (TiO)2) Any one of them.
The light absorbing layer 4 is an IGZO film doped with hydrogen. The IGZO material forms deep-level defects due to the doping of hydrogen, and the band gap of the IGZO material is smaller than or equal to the photon energy of visible light, so that when the IGZO film doped with hydrogen is used as a light absorption layer, the light absorption layer can absorb photons of the visible light, electrons are generated, and a photocurrent is formed under the action of an external electric field.
In some preferred embodiments, the light absorbing layer 4 has a thickness of 5-50 nm.
The channel layer 5 may be any one selected from an IGZO film, an IGZO film doped with hydrogen, an amorphous silicon film, a graphene film, and a molybdenum disulfide film.
In some preferred embodiments, the channel layer has a thickness of 10-150 nm.
The source electrode 6 may be selected from a nickel electrode or an aluminum electrode.
Wherein the drain electrode 7 may be selected from a nickel electrode or an aluminum electrode.
In general terms: the embodiment of the invention prepares the hydrogen-doped IGZO with the deep-level defects, so that the band gap of the IGZO is less than or equal to the photon energy of visible light, and further, the IGZO can generate good response to the visible light, and the problem of low response of common IGZO to the visible light is solved.
The embodiment of the invention manufactures the phototransistor with the light absorption layer doped with hydrogen, and the material of the light absorption layer comprises the IGZO doped with hydrogen, so that the novel light absorption layer can generate good response to visible light, the phototransistor can realize the purpose of detecting in a visible light wave band, and the problem that the existing IGZO type phototransistor is difficult to apply to the field of visible light detection is solved.
The above-mentioned hydrogen-doped IGZO and the preparation method thereof, the phototransistor and the manufacturing method thereof according to the present invention will be described below with reference to specific examples, and it will be understood by those skilled in the art that the following examples are only specific examples of the present invention, and are not intended to limit the entirety thereof. The specific techniques or conditions are not indicated in the examples, and the reagents or apparatuses used are not indicated in the manufacturer's instructions, and are all conventional products commercially available, according to the conventional techniques or conditions in the art or according to the product specifications.
Example 1
(1) Substrate selection silicon wafer Substrate (SiO)2and/Si), cleaning the substrate and drying for later use.
(2) And growing a gate electrode. And (3) putting the cleaned silicon wafer substrate into a magnetron sputtering reaction cavity, and growing a molybdenum electrode layer with the thickness of 1 micrometer by direct current sputtering. In order to improve the adhesion and conductivity, when the Mo electrode is grown, the Mo electrode is grown in two steps: firstly, growing a loose Mo layer under high pressure (2.8Pa, sputtering for 19 circles under 350W power) to improve the adhesion with a substrate; and secondly, growing Mo of the dense layer under low pressure (0.3Pa gas pressure and 9 turns of 1000W power sputtering) to optimize the conductivity of the Mo electrode.
(3) And growing a gate dielectric layer. Putting the sample obtained in the step (2) into Atomic Layer Deposition (ALD) equipment, sequentially introducing an aluminum source and an oxygen source, and depositing Al with the thickness of 40nm at room temperature2O3And a gate dielectric layer.
(4-1) growing a light absorption layer, putting the sample obtained in the step (3) into a magnetron sputtering reaction chamber, and firstly pumping the pressure of the cavity before sputtering to 5 × 10 by a mechanical pump and a molecular pump-5Pa, room temperature, introducing Ar and H into the cavity during sputtering2And controlling Ar: h2The volume ratio of the metal oxide layer to the metal oxide layer is about 96:4, the cavity pressure of the sputtering cavity is regulated to 2Pa for sputtering glow starting, then the working pressure of the cavity is controlled to 0.9Pa, sputtering is carried out under 100W, and the hydrogen-doped IGZO thin film with the thickness of 30nm is formed. The target material used for sputtering is indium gallium zinc oxide, and the atomic ratio of In to Ga to Zn to O In the target material is 1:1:1: 4.
(4-2) annealing the light-absorbing layer. Annealing the IGZO film doped with hydrogen in a tubular annealing furnace in an annealing gas environment of H2And N2In which H is2The volume ratio of (A) is 4%, the pressure is 10kPa, and the annealing temperature is 100 ℃.
(5) And growing a channel layer. And (4) growing a second IGZO thin film with the thickness of 100nm by adopting the method in the step (4-1) and appropriately changing parameters.
And spin-coating a layer of positive photoresist film on the surface of the second IGZO film at the speed of 3000r/min, and carrying out photoetching development under the assistance of a photoetching plate to obtain a channel pattern. And wet etching in a dilute hydrochloric acid solution for 6min, and removing residual photoresist on the upper surface of the channel by using acetone to obtain the channel.
(6) And growing a source electrode and a drain electrode. And under the condition of completing the first 5 steps, growing a source electrode and a drain electrode of the transistor, and evaporating a layer of Ni electrode on the transistor by using electron beam evaporation to obtain the phototransistor.
The phototransistor manufactured by the embodiment comprises a silicon wafer substrate, a molybdenum electrode layer with the thickness of 1 micron and Al with the thickness of 40nm which are sequentially overlapped2O3The transistor comprises a gate dielectric, a 30nm thick hydrogen-doped IGZO light absorption layer, a 100nm thick hydrogen-doped IGZO channel layer and a source and drain electrode layer, wherein the source and drain electrode layer is composed of a Ni source electrode and a Ni drain electrode which are spaced from each other.
Comparative example 1
The IGZO type phototransistor was produced by using the same production steps and process parameters as those in example 1. The same parts are not described again, and the comparative example is different from example 1 in that: in the step (4-1), only Ar is introduced during sputtering, and H is not introduced2(ii) a In the step (4-2), the annealing gas atmosphere is high purity N2Without hydrogen.
The photoelectric transistor manufactured by the comparative example comprises a silicon chip substrate, a molybdenum electrode layer with the thickness of 1 mu m and Al with the thickness of 40nm which are arranged in a one-time overlapping way2O3The transistor comprises a gate medium, an IGZO light absorption layer with the thickness of 30nm, a channel layer with the thickness of 100nm and a source and drain electrode layer, wherein the source and drain electrode layer is a source electrode and a drain electrode which are spaced from each other.
The phototransistor of the above example and comparative example was subjected to characterization test, and the test results and analysis were as follows:
current responsivity curves of the phototransistors manufactured in example 1 and comparative example 1 in the wavelength band of 300nm to 700nm are shown in FIG. 2, wherein the current responsivity is shown in the R tableThe unit is A.W-1. As can be seen from fig. 2, the phototransistor having the hydrogen-doped light absorption layer manufactured in example 1 has a higher current responsivity in the wavelength band of 300nm to 500nm, which is significantly better than the phototransistor in comparative example 1.
The transfer characteristics of the phototransistors prepared in example 1 and comparative example 1 under the irradiation of light with a wavelength of 450nm and different powers are shown in fig. 3 and 4, respectively. As can be seen from fig. 3, under different power illumination, the photo-transistor using the IGZO thin film doped with hydrogen as the light absorption layer generates different degrees of response to different power illumination energies, and the response current is larger as the illumination intensity increases; as can be seen from fig. 4, the phototransistor using the common (non-hydrogen-doped) IGZO thin film as the light absorbing layer did not respond significantly under the illumination condition with a wavelength of 450nm, and the degree of photoresponse did not change significantly after the power of illumination was changed.
The test results of the above example 1 and the comparative example 1 show that the ordinary IGZO type phototransistor has no response to visible light basically, and the phototransistor manufactured in the example 1 of the present invention can generate good response to visible light because the light absorption layer is the IGZO thin film doped with hydrogen, thereby realizing the application of the IGZO type phototransistor in the field of visible light detection. The reason for this is that the band gap of the hydrogen-doped IGZO material is smaller than the photon energy of visible light, and thus can absorb photons of visible light and generate electrons, and a photocurrent is formed under the action of an external electric field.
While the invention has been shown and described with reference to certain embodiments, those skilled in the art will understand that: various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims and their equivalents.
Claims (12)
1. A preparation method of a hydrogen-doped indium gallium zinc oxide film layer is characterized by comprising the following steps: preparing a hydrogen-doped indium gallium zinc oxide film layer by adopting a film coating process in a first gas atmosphere; the first gas atmosphere comprises hydrogen, and the band gap width of the hydrogen-doped indium gallium zinc oxide film layer is smaller than or equal to the photon energy of visible light.
2. The method of claim 1, wherein the first gas atmosphere further comprises an inert gas, and a volume ratio of the hydrogen gas to the inert gas is less than or equal to 10: 90.
3. The method of manufacturing according to claim 1 or 2, wherein the: under the atmosphere of the first gas, the step of preparing the indium gallium zinc oxide film layer doped with hydrogen by adopting a coating process also comprises the following steps: and annealing the hydrogen-doped indium gallium zinc oxide film layer.
4. The method of claim 3, wherein the step of annealing the hydrogen-doped InGaZn oxide film layer comprises: and annealing the hydrogen-doped indium gallium zinc oxide film layer in a mixed gas atmosphere, wherein the mixed gas comprises hydrogen and inert gas, and the volume ratio of the hydrogen to the inert gas is less than or equal to 10: 90.
5. A hydrogen-doped InGaZn oxide film prepared by the method of any one of claims 1 to 4.
6. Use of the hydrogen doped indium gallium zinc oxide film of claim 5 in a semiconductor device.
7. A manufacturing method of a transistor is characterized by comprising the following steps of manufacturing a gate electrode layer, a gate dielectric layer, a hydrogen-doped indium gallium zinc oxide film layer, a channel layer, a source electrode and a drain electrode, wherein the method for manufacturing the hydrogen-doped indium gallium zinc oxide film layer is the manufacturing method of any one of claims 1 to 4.
8. The method of claim 7, wherein the steps of forming the gate electrode layer, the gate dielectric layer, the hydrogen-doped InGaZnO film layer, the channel layer, the source electrode, and the drain electrode comprise:
forming the gate electrode layer over a substrate;
forming a gate dielectric layer on the gate electrode layer;
forming the hydrogen-doped indium gallium zinc oxide film layer on the gate dielectric layer by adopting the preparation method of the hydrogen-doped indium gallium zinc oxide film layer as claimed in any one of claims 1 to 4;
forming the channel layer on the hydrogen-doped indium gallium zinc oxide film layer;
forming the spaced source electrode and the drain electrode on the channel layer.
9. A transistor fabricated by the fabrication method of claim 7 or 8.
10. A transistor, comprising: gate electrode layer, gate dielectric layer, channel layer, source electrode and drain electrode, characterized in that, the transistor still includes: and a light absorbing layer disposed above or below at least one of the gate electrode layer, the gate dielectric layer, the channel layer, the source electrode, and the drain electrode, wherein a band gap width of the light absorbing layer is less than or equal to a photon energy of visible light.
11. The transistor according to claim 10, wherein the gate electrode layer is provided over a substrate;
the gate dielectric layer is arranged on the gate electrode layer;
the light absorption layer is arranged on the gate dielectric layer;
the channel layer is disposed on the light absorbing layer;
the source electrode and the drain electrode are disposed on the channel layer, and the source electrode and the drain electrode are spaced apart from each other.
12. The transistor of claim 10 or 11, wherein the light-absorbing layer is the hydrogen-doped indium gallium zinc oxide film of claim 5.
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