CN110277418B - Pixel unit of perovskite image sensor and preparation method thereof - Google Patents
Pixel unit of perovskite image sensor and preparation method thereof Download PDFInfo
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- CN110277418B CN110277418B CN201910546230.0A CN201910546230A CN110277418B CN 110277418 B CN110277418 B CN 110277418B CN 201910546230 A CN201910546230 A CN 201910546230A CN 110277418 B CN110277418 B CN 110277418B
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/14603—Special geometry or disposition of pixel-elements, address-lines or gate-electrodes
- H01L27/14605—Structural or functional details relating to the position of the pixel elements, e.g. smaller pixel elements in the center of the imager compared to pixel elements at the periphery
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14601—Structural or functional details thereof
- H01L27/1462—Coatings
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L27/00—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate
- H01L27/14—Devices consisting of a plurality of semiconductor or other solid-state components formed in or on a common substrate including semiconductor components 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
- H01L27/144—Devices controlled by radiation
- H01L27/146—Imager structures
- H01L27/14683—Processes or apparatus peculiar to the manufacture or treatment of these devices or parts thereof
Abstract
The embodiment of the invention provides a pixel unit of an image sensor based on a perovskite photosensitive material and a preparation method thereof, wherein the photosensitive pixel unit comprises a metal oxide thin film transistor and an organic-inorganic hybrid perovskite photodiode, the metal oxide thin film transistor comprises a base substrate, a grid metal electrode, a grid insulating layer, a metal oxide semiconductor thin film, a source drain metal electrode, a silicon dioxide protective layer and a hydrophobic layer thin film, and the organic-inorganic hybrid perovskite photodiode comprises an Indium Tin Oxide (ITO) electrode, a pattern electron transmission layer, an organic-inorganic hybrid perovskite material layer, a charge transmission layer and a metal electrode.
Description
Technical Field
The invention relates to the field of optical detectors, in particular to a perovskite infrared pixel unit device and a preparation method thereof.
Background
The metal oxide semiconductor thin film transistor, especially an Indium Gallium Zinc Oxide (IGZO) thin film transistor has the characteristics of stability, high mobility, transparency, good uniformity and the like, and is widely applied to display panel arrays and detector arrays, but the IGZO material has no obvious response to a visible light waveband of more than 420nm due to the fact that the IGZO material is large in forbidden band width (>3 eV). The organic-inorganic hybrid perovskite material has the characteristics of wide light absorption range, high carrier mobility, high carrier generation speed, long carrier diffusion length, long carrier service life and the like, and the organic-inorganic hybrid perovskite material has wide application in the field of photoelectric detectors due to the excellent light absorption characteristic. In order to realize better infrared photoelectric detection effect, a novel infrared photoelectric detector can be prepared by combining an organic-inorganic hybrid infrared detection perovskite material with a metal oxide transistor.
In the process of implementing the invention, the inventor finds that at least the following problems exist in the prior art: the performance of the perovskite photodiode is deteriorated after patterning by organic-inorganic hybrid infrared detection; the solution process of the photodiode can cause the performance degradation of the metal oxide thin film transistor, which is characterized by the increase of dark current, the increase of subthreshold swing and the increase of the absolute value of threshold voltage.
Disclosure of Invention
The embodiment of the invention provides a pixel unit structure of a perovskite image sensor and a preparation method thereof. The scheme provides the pixel unit with low dark current, high response speed and wide spectral response, and the preparation process is simple, the success rate of devices is high, and the potential is great in the field of photodetectors.
In one aspect, an embodiment of the present invention provides a perovskite image sensing pixel unit, where the pixel unit includes: the photoelectric device comprises a base substrate, a grid metal electrode, a metal oxide semiconductor thin film, a source drain metal electrode and a hydrophobic thin film, wherein the grid metal electrode, the metal oxide semiconductor thin film and the source drain metal electrode are positioned on the base substrate, the hydrophobic thin film covers the substrate and the rest parts of the device except an organic-inorganic hybrid infrared detection perovskite photoelectric diode, a photoelectric diode is manufactured on an Indium Tin Oxide (ITO) electrode which is not covered by perfluoro resin CYTOP, the photoelectric diode comprises a charge transmission layer, an organic-inorganic hybrid infrared detection perovskite material layer, a charge transmission layer and a photoelectric diode metal electrode, and the projection area of the photoelectric diode metal electrode is equal to or smaller than the area of the charge transmission layer.
On the other hand, the embodiment of the invention provides a preparation method of the perovskite image sensor pixel unit, and the preparation method of the perovskite infrared pixel unit comprises the following steps:
depositing a gate metal electrode and a gate insulating layer on the base substrate, the gate insulating layer completely covering the gate metal electrode;
depositing a metal oxide semiconductor film on the gate insulating layer, and patterning by using a photoetching technology;
depositing source and drain electrode metal on the metal oxide semiconductor film, and leaking out the metal oxide semiconductor film at the channel part;
covering a hydrophobic film on the base substrate and the rest parts of the device except the Indium Tin Oxide (ITO) electrode led out from the drain terminal of the metal oxide semiconductor thin film transistor, wherein the hydrophobic film and the Indium Tin Oxide (ITO) electrode are covered by a small part;
preparing a pattern electron transmission layer on the Indium Tin Oxide (ITO) electrode uncovered by the perfluoro resin CYTOP;
preparing a patterned organic-inorganic hybrid infrared detection perovskite layer on the charge transport layer, the charge transport layer separating at least the patterned organic-inorganic hybrid infrared detection perovskite layer from the Indium Tin Oxide (ITO) electrode;
preparing a charge transport layer on the patterned organic-inorganic hybrid infrared detection perovskite layer, wherein the charge transport layer at least separates the organic-inorganic hybrid infrared detection perovskite layer from the photodiode metal electrode;
preparing a photodiode metal electrode on the charge transport layer, wherein the projection area of the photodiode metal electrode is equal to or smaller than the area of the charge transport layer;
the technical scheme has the following beneficial effects: the embodiment of the invention adopts the metal oxide semiconductor as the channel material of the pixel unit, the organic-inorganic hybrid infrared detection perovskite as the light absorption layer material, the Indium Tin Oxide (ITO) electrode led out from the drain end of the metal oxide semiconductor thin film transistor is used for connecting the organic-inorganic hybrid perovskite photodiode with the metal oxide thin film transistor in series to prepare the transistor with the separation structure of the metal oxide semiconductor thin film transistor and the infrared detection perovskite photodiode, the characteristics of stability, high mobility, transparency and good uniformity of the metal oxide semiconductor represented by Indium Gallium Zinc Oxide (IGZO) are utilized, the light absorption material with excellent performance of the organic-inorganic hybrid infrared detection perovskite is adopted, the characteristics of strong infrared absorption property, high mobility and high carrier generation speed of the light absorption material are utilized to overcome the defect that the forbidden bandwidth of the metal oxide semiconductor material represented by Indium Gallium Zinc Oxide (IGZO) is larger, the infrared light cannot be effectively absorbed, and the forbidden band width can be adjusted by adjusting the bromine Br content in the perovskite. The hydrophobic layer material separates each laminated material of the organic-inorganic hybrid infrared detection perovskite photodiode from the metal oxide thin film transistor, and leakage current caused by the organic-inorganic hybrid perovskite material appearing above the metal oxide thin film is avoided. Therefore, the perovskite infrared photoelectric detector combined with the metal oxide semiconductor thin film transistor and the organic-inorganic hybrid infrared detection perovskite photoelectric diode and connected in series with the Indium Tin Oxide (ITO) electrode led out from the drain terminal of the metal oxide semiconductor thin film transistor can be fully combined with a pixel unit prepared by high mobility of a metal oxide semiconductor and high light absorption performance of a perovskite material, and has the technical effects of low dark current, high response speed and wide spectral response; the preparation method provided by the embodiment of the invention has good compatibility with the current process platform, the preparation process of the device is simple, and the success rate of the device is high.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the technical solutions in the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a schematic structural diagram of perovskite infrared pixel units in examples 1 and 2 of the invention;
FIG. 2 is a flow chart of a perovskite infrared pixel unit preparation method according to an embodiment of the invention;
FIG. 3 is a schematic structural diagram of a substrate after a gate and a gate insulating layer are deposited thereon according to embodiment 1 of the present invention;
FIG. 4 is a schematic structural diagram of a gate insulation layer with a metal oxide semiconductor thin film deposited thereon according to embodiment 1 of the present invention;
FIG. 5 is a schematic structural diagram of a metal oxide semiconductor film according to embodiment 1 of the present invention after source and drain metal electrodes are deposited thereon;
FIG. 6 is a schematic structural diagram of the base substrate and the rest of the device covered with the passivation layer and the hydrophobic film except the ITO electrode led out from the drain terminal of the MOS TFT in accordance with embodiment 1 of the present invention;
FIG. 7 is a schematic structural diagram of the ITO electrode uncovered by perfluororesin CYTOP and having a patterned electron transport layer thereon according to example 1 of the present invention;
FIG. 8 is a schematic structural view after a patterned organic-inorganic hybrid infrared detection perovskite layer is prepared on a patterned electron transport layer in example 1 of the present invention;
FIG. 9 is a schematic structural view after a charge transport layer is prepared on an organic-inorganic hybrid infrared detecting perovskite layer in example 1 of the present invention;
FIG. 10 is a schematic structural diagram of example 1 of the present invention after preparing a metal electrode of an organic-inorganic hybrid perovskite photodiode on a charge transport layer;
FIG. 11 is a graph of transfer characteristics of perovskite infrared pixel cells of embodiments of the present invention under light-dark conditions.
Wherein, in the figure: the manufacturing method comprises the following steps of 1-a base substrate, 2-a grid metal electrode, 3-a grid insulating layer, 4-a metal oxide semiconductor thin film, 5-a source drain metal electrode, 6-a silicon dioxide protective layer, 7-a hydrophobic layer thin film, 8-an ITO electrode, 9-a graphic electron transmission layer, 10-an organic-inorganic hybrid perovskite material layer, 11-a charge transmission layer and 12-a metal electrode.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
As shown in fig. 1, which is a schematic view of a perovskite infrared pixel unit in embodiment 1 of the present invention, the perovskite infrared pixel unit includes a base substrate 1, a gate metal electrode 2, a gate insulating layer 3, a metal oxide semiconductor thin film 4, source and drain metal electrodes 5, a silicon dioxide protective layer 6, a hydrophobic layer thin film 7, an indium tin oxide ITO electrode 8, a pattern electron transport layer 9, an organic-inorganic hybrid perovskite material layer 10, a charge transport layer 11, and a metal electrode 12; wherein, the grid metal electrode 2 is positioned on the base substrate 1, positioned on the base substrate 1 and wrapped by the grid metal electrode 2, the metal oxide semiconductor film 4, the indium tin oxide ITO electrode 8, the source drain metal electrode 5 and the silicon dioxide protective layer 6 are positioned on the grid insulating layer 3, wherein the source drain metal electrode 5 and the bottom of the metal oxide semiconductor film 4 are positioned on the same plane, the source drain metal electrode 5 partially covers the metal oxide semiconductor film 4, the pattern electronic transmission layer 9 is positioned on the indium tin oxide ITO electrode 8, the silicon dioxide protective layer 6 wraps the metal oxide semiconductor film 4, the source drain metal electrode 5, the indium tin oxide ITO electrode 8 and the pattern electronic transmission layer 9, wherein the silicon dioxide protective layer wraps the top of the metal oxide semiconductor film and wraps the left side and the right side of the pattern electron transmission layer; the hydrophobic layer film 7 is positioned on the silicon dioxide protective layer 6, the organic-inorganic hybrid perovskite material layer 10 is positioned on the pattern electron transmission layer 9, the bottom area of the organic-inorganic hybrid perovskite material layer 10 is equal to that of the pattern electron transmission layer 9, the charge transmission layer 11 is positioned on the organic-inorganic hybrid perovskite material layer 10, the bottom area of the charge transmission layer 11 is equal to that of the organic-inorganic hybrid perovskite material layer 10, the metal electrode 12 partially covers the charge transmission layer 11, and the bottom area of the metal electrode 12 is smaller than the top area of the charge transmission layer 11; wherein, the silicon dioxide protective layer 6 partially wraps the left and right sides of the organic-inorganic hybrid perovskite material layer 10, the hydrophobic layer film 7 wraps the left and right sides of the charge transmission layer 11, and the metal electrode 12 is exposed outside the hydrophobic layer film 7; the source and drain metal electrodes 5 are L-shaped electrodes and comprise a first L-shaped electrode and a second L-shaped electrode, the second L-shaped electrode comprises a second transverse end and a second vertical end, the second vertical end is laterally contacted with the Indium Tin Oxide (ITO) electrode 8, and the second transverse end covers the metal oxide semiconductor film 4; the top surface of the organic-inorganic hybrid perovskite material layer 10 is higher than the top surface of the silicon dioxide protective layer 6, and the top surface of the charge transport layer 11 is lower than the top surface of the hydrophobic layer film 7;
preferably, the base substrate 1 is made of: glass, polyimide PI, polyethylene terephthalate PET or polyethylene naphthalate PEN.
Preferably, the source-drain metal electrode 5 and the metal oxide semiconductor film 4 are on the same plane; the gate metal electrode 2 is completely covered by the gate insulating layer 3, and the metal oxide semiconductor film 4 is deposited on the surface of the gate insulating layer 3.
Preferably, the material of the hydrophobic layer thin film 7 includes: perfluororesin CYTOP;
the material of the charge transport layer 9 includes: tin oxide SnO2Titanium oxide TiO2；
The thickness of the charge transport layer 9 is 10nm to 90 nm;
the graphical organic-inorganic hybrid infrared detection perovskite material layer 10 is positioned right above the graphical electronic transmission layer 9, and the projection area is equal to the exposed area of the hydrophobic layer thin film 7;
the chemical formula of the material of the patterned organic-inorganic hybrid infrared detection perovskite material layer 10 is ABX3A comprises ABX3A includes methylamine ion CH3NH3 +Formamidine ion NH2CHNH2 +Cesium ion CS+Rb ion (Rb)+And a mixture of these cations, B comprising the lead ion Pb2+Sn ion Sn2+Bismuth ion Bi2+Europium ion Eu2+And a mixture of these cations, wherein Sn is2+Is an essential element, and the proportion of Sn ions in B site cation elements is between 40 and 60 percent; x comprises iodide ion I-Chloride ion Cl-Or bromide ion Br-(ii) a The perovskite has a light absorption capacity of 300nm to 1100 nm.
The thickness of the graphical organic-inorganic hybrid infrared detection perovskite 10 is 20nm to 2 um;
the material of the charge transport layer 11 includes: polymer of 3-hexylthiophene P3HT, 2,7, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene Spiro-MeOTAD, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] PTAA;
the thickness of the charge transport layer 11 is 10nm to 90 nm;
the material of the metal electrode 12 includes: gold, silver, copper;
the material of the metal oxide semiconductor thin film 4 includes: indium gallium zinc oxide IGZO, indium zinc tin oxide IZTO, aluminum-doped zinc oxide AZO, zinc tin oxide ZTO, magnesium zinc oxide MZO;
the thickness of the metal oxide semiconductor film 4 is 10nm to 100 nm;
the materials of the silicon dioxide protective layer 6 include: polymethyl methacrylate PMMA, perfluoro resin CYTOP, silicon oxide SiOxSilicon nitride SiNxAnd alumina Al2O3；
The thickness of the passivation layer is 20nm to 900 nm. Preferably, the gate metal electrode 2 and the source drain metal electrode 5 are molybdenum, gold, silver, aluminum, copper material electrodes;
the grid metal electrode 2 and the source drain metal electrode 5 are in a strip block shape or an interdigital block shape;
the thickness of the grid metal electrode 2 and the thickness of the source drain metal electrode 5 are 30nm to 200 nm;
the length of a channel formed by the source drain metal electrode 5 is 1um to 100um, and the width is 1um to 1000 um; the above-mentioned
The gate insulating layer 3 is silicon oxide SiOxSilicon nitride SiNxAluminum oxide Al2O3Hafnium oxide HfO2A material;
the thickness of the gate insulating layer 3 is 50nm to 500 nm.
Corresponding to the above method embodiment, as shown in fig. 3, a gate metal electrode 2 and a gate insulating layer 3 are deposited on the base substrate, and the gate insulating layer 3 completely covers the gate metal electrode 2;
depositing a metal oxide semiconductor film 4 and a source drain metal electrode 5 on the gate insulating layer 3, wherein the source drain metal electrode 5 partially covers the metal oxide semiconductor film 4 and leaks out of the metal oxide semiconductor at the channel part;
the hydrophobic layer film 7 will cover the perovskite photodiode region except for the part completely;
the graphic electronic transmission layer 9, the organic-inorganic hybrid infrared detection perovskite 10, the charge transmission layer 11 and the perovskite photodiode metal electrode 12 are arranged on the ITO electrode 8 uncovered by the hydrophobic layer film 7, or the area of the perovskite photodiode metal electrode 12 is slightly smaller than that of the ITO electrode 8 uncovered by the hydrophobic layer film 7.
Preferably, a gate metal electrode 2 is deposited on the base substrate 1;
a gate insulating layer 3 is deposited on the gate metal electrode 2.
Preferably, the gate metal electrode 2 is grown on the base substrate 1 by a magnetron sputtering method or a vacuum evaporation method, and then a gate pattern is formed by a photolithography process;
growing the gate insulating layer 3 on the gate metal electrode 2 by adopting a magnetron sputtering method or a chemical vapor deposition method;
directly growing the metal oxide semiconductor film 4 on the grid insulating layer 3 by adopting a magnetron sputtering method or a solution processing method, and then forming a block-shaped active region pattern by a photoetching process; and annealing the device in an oxygen atmosphere, a nitrogen atmosphere or an air atmosphere at the temperature of 100-450 ℃ for 0.5-4 hours.
And directly growing the source and drain metal electrodes 5 on a base substrate by adopting a magnetron sputtering method or a vacuum evaporation method, and then forming a source and drain metal electrode pattern by a photoetching process, wherein the active region of the metal oxide semiconductor film 4 and the source and drain metal electrodes 5 are overlapped to a certain extent.
Preferably, a solution processing method and a photolithography process or a plasma etching method are used to prepare the hydrophobic layer thin film 7 except for the perovskite photodiode; preparing a charge transmission layer 9 on the ITO electrode 8 uncovered by the hydrophobic layer film 7 by using a solution processing method; preparing a layer of graphical organic-inorganic hybrid perovskite material layer 10 on the charge transmission layer 9 by adopting a solution spin coating method, a blade coating method, a spraying method, a vacuum evaporation method, a chemical vapor deposition method, a screen printing method or a roll-to-roll printing method, wherein the projection area of the graphical organic-inorganic hybrid perovskite material layer 10 is not more than the area of the ITO electrode 8; preparing a charge transport layer 11 on the organic-inorganic hybrid perovskite material layer 10 by a solution spin coating method, wherein the charge transport layer 11 covers the pattern electron transport layer 9 and the organic-inorganic hybrid perovskite material layer 10 completely. The metal electrode 12 is manufactured by a magnetron sputtering method or a vacuum evaporation method, and the projection area of the metal electrode 12 is equal to or smaller than the area of the charge transmission layer 11.
As shown in fig. 3, a flowchart of a method for manufacturing a perovskite infrared pixel unit according to an embodiment of the present invention is shown, where the method includes:
201. depositing a gate metal electrode 2 and a gate insulating layer 3 on the base substrate, wherein the gate insulating layer 3 completely covers the gate electrode 2; referring to fig. 3, fig. 3 is a schematic structural diagram of a gate metal electrode 2 and a gate insulating layer 3 deposited in embodiment 1 of the present invention, where the source and drain metal electrodes 4 are in a bar shape or an interdigital shape.
202. Depositing a metal oxide semiconductor film 4 on the source gate insulating layer 3; referring to fig. 4, fig. 4 is a schematic structural diagram of a metal oxide semiconductor film deposited according to embodiment 1 of the present invention.
203. Depositing a source drain metal electrode 5 on the metal oxide semiconductor film 4, and leading out an ITO electrode 8 at the drain end of the metal oxide film transistor; referring to fig. 5, fig. 5 is a schematic structural diagram of a source-drain metal electrode 4 deposited in embodiment 1 of the present invention, where the source-drain metal electrode 4 is in a bar shape or an interdigital shape, and the source-drain metal electrode 4 is located at two ends of the surface of the metal oxide semiconductor thin film 4 and leaks out of a channel portion, as shown in fig. 5.
204. Covering a silicon dioxide protective layer 6 and a hydrophobic layer film 7 on the base substrate and the rest parts of the device except the ITO electrode 8 led out from the drain terminal of the metal oxide semiconductor thin film transistor; referring to fig. 6, fig. 6 is a schematic structural diagram of embodiment 1 after covering a silicon dioxide protection layer 6 and a hydrophobic layer film 7 on a base substrate and the rest of the device except an ITO electrode 8 led out from a drain terminal of the mos thin film transistor.
205. Preparing a pattern electron transmission layer 9 on the ITO electrode 8 uncovered by the hydrophobic layer film 7; referring to fig. 7, fig. 7 is a schematic structural diagram of embodiment 1 of the present invention after a patterned electron transport layer 9 is prepared on an ITO electrode 8 uncovered by the hydrophobic layer film 7.
206. Preparing a patterned organic-inorganic hybrid perovskite material layer 10 on the patterned electron transport layer 9, wherein the patterned electron transport layer 9 at least separates the patterned organic-inorganic hybrid perovskite material layer 10 from the ITO electrode 8; referring to fig. 8, fig. 8 is a schematic structural diagram after a patterned organic-inorganic hybrid perovskite material layer is deposited on a charge transport layer in example 1 of the present invention.
207. A charge transport layer 11 is formed on the organic-inorganic hybrid perovskite material layer 10, please refer to fig. 9, and fig. 9 is a schematic structural diagram of the organic-inorganic hybrid perovskite material layer 10 after the charge transport layer 11 is formed on the organic-inorganic hybrid perovskite material layer 10 in the embodiment 1 of the present invention.
208. Referring to fig. 10, an organic-inorganic hybrid perovskite photodiode metal electrode 12 is prepared on the charge transport layer 11, and fig. 10 is a schematic structural diagram of the organic-inorganic hybrid perovskite photodiode metal electrode 12 prepared on the charge transport layer 11 in example 1 of the present invention.
The technical scheme has the following beneficial effects: the embodiment of the invention adopts the metal oxide semiconductor as the channel material of the pixel unit, the organic-inorganic hybrid infrared detection perovskite as the light absorption layer material, the ITO electrode led out from the drain terminal of the metal oxide semiconductor thin film transistor connects the organic-inorganic hybrid perovskite photodiode with the metal oxide thin film transistor in series to prepare the transistor with the separation structure of the metal oxide semiconductor thin film transistor and the infrared detection perovskite photodiode, not only utilizes the characteristics of stability, high mobility, transparency and good uniformity of the metal oxide semiconductor represented by IGZO, but also adopts the light absorption material with excellent performance of the organic-inorganic hybrid infrared detection perovskite, overcomes the defects of larger forbidden bandwidth of the metal oxide semiconductor material represented by IGZO by utilizing the characteristics of strong infrared absorption property, high mobility and high carrier generation speed, the defect of no effective absorption of infrared light, and the forbidden band width can be adjusted by adjusting the Br content in the perovskite. The hydrophobic layer material separates each laminated material of the organic-inorganic hybrid infrared detection perovskite photodiode from the metal oxide thin film transistor, and leakage current caused by the organic-inorganic hybrid perovskite material appearing above the metal oxide thin film is avoided. Therefore, the perovskite infrared photoelectric detector which is combined with the metal oxide semiconductor thin film transistor and the organic-inorganic hybrid infrared detection perovskite photoelectric diode and is connected in series with the ITO electrode led out from the drain end of the metal oxide semiconductor thin film transistor can be fully combined with a pixel unit prepared by the high mobility of the metal oxide semiconductor and the high light absorption performance of the perovskite material, and has the technical effects of low dark current, high response speed and wide spectral response; the preparation method provided by the embodiment of the invention has good compatibility with the current process platform.
The technical solution of the embodiment of the present invention will be described in detail below with reference to the accompanying drawings and embodiments, and the preparation method of the novel perovskite infrared pixel unit of the application embodiment of the present invention is briefly described as follows:
1. a glass substrate is selected as a substrate material, and the substrate is respectively subjected to ultrasonic treatment in deionized water, acetone and alcohol for 15 minutes before the experiment.
2. Preparation of grid molybdenum Mo metal electrode
(1) Preparation before magnetron sputtering
And spin-coating photoresist, and exposing the effective region by utilizing photoetching, wherein the ineffective region is covered by the photoresist.
(2) Preparation of molybdenum Mo metal electrode
The photoetched substrate is placed into a magnetron sputtering platform, and when the vacuum in a sputtering platform box reaches 9.9 multiplied by 10-4And when Pa is needed, introducing argon Ar to ensure that the vacuum degree in the cavity is stabilized at 0.36Pa, sputtering for 150s by using 80W of direct-current power supply power to obtain a Mo film with the thickness of 120nm, and forming a grid electrode pattern by stripping.
3. Silicon dioxide SiO of gate insulating layer2Preparation of
Putting the sample wafer into a reaction chamber of a plasma enhanced chemical vapor deposition PECVD system, pumping the reaction chamber to high vacuum, raising the temperature of the reaction chamber to 300 ℃, ensuring that the radio frequency power is 30W, and simultaneously introducing SiH with the flow rate of 100sccm into the reaction chamber4And N of 400sccm2O, the pressure is controlled to be 0.7Pa, and SiO with the thickness of 200nm is grown2A film.
4. Preparation of active layer Indium Gallium Zinc Oxide (IGZO)
(1) Preparation of Indium Gallium Zinc Oxide (IGZO) thin film
Putting the substrate into a magnetron sputtering platform, and when the vacuum in a sputtering platform box reaches 5 multiplied by 10-4When Pa, argon Ar and oxygen O are introduced2The flow ratio is 47: 3, and the indium gallium zinc oxide IGZO thin film with the thickness of 40nm is obtained by sputtering for 300s by using the power of a direct current power supply of 100W.
(2) Patterning of Indium Gallium Zinc Oxide (IGZO)
Spin-coating photoresist, photoetching and etching the Indium Gallium Zinc Oxide (IGZO) film by using dilute hydrochloric acid; and ultrasonically removing the photoresist by using acetone.
5. Annealing treatment
And (3) annealing the transistor device with the manufactured metal oxide thin film for 1 hour at 200 ℃ under the condition of pure oxygen.
6. Preparation of source drain metal electrode Mo
(1) Preparation before magnetron sputtering
And spin-coating photoresist, and exposing the effective region by utilizing photoetching, wherein the ineffective region is covered by the photoresist.
(2) Preparation of Mo electrode
The photoetched substrate is placed into a magnetron sputtering platform, and when the vacuum in a sputtering platform box reaches 9.9 multiplied by 10-4And when Pa is needed, introducing argon Ar to ensure that the vacuum degree in the cavity is stabilized at 0.36Pa, sputtering for 150s by using the power of a direct current power supply of 80W to obtain a Mo film with the thickness of 120nm, and forming a source-drain pattern by stripping.
7. Preparation of passivation layer and hydrophobic layer perfluoro resin CYTOP
(1) Preparation of Perfluororesin CYTOP solution
The proportion of the perfluororesin CYTOP to solvent is 1:10, and the mixture is stirred for 1 hour at normal temperature.
(2) Preparation of photoresist sacrificial layer
And spin-coating a photoresist, and covering the photoresist on the metal oxide semiconductor film only by utilizing the photoetching, wherein the photoresist does not exist at the rest positions of the substrate and the device.
(3) The preparation of the patterned hydrophobic layer perfluororesin CYTOP is completed
And uniformly spin-coating and adsorbing the stirred CYTOP solution on the surface of the substrate comprising the photoresist sacrificial layer at the rotating speed of 3000rpm for 60s, annealing at the heating table at 100 ℃ for 30s, then putting the CYTOP solution into an acetone solution, performing ultrasonic treatment for 10s, soaking for 10min, and then annealing at the heating table at 100 ℃ for 10min to obtain a patterned CYTOP hydrophobic layer with the thickness of 20nm to 30nm, wherein the CYTOP hydrophobic layer completely covers the substrate except the metal oxide semiconductor film and the rest part of the device.
8. Charge transport layer tin oxide SnO2Layer preparation
(1) Tin oxide SnO2Preparation of the solution
SnO2The colloidal dispersion was mixed with deionized water at a volume ratio of 1: 6.5.
(2) Charge transport layer tin oxide SnO2Preparation of the layer
Mixing uniformly tin oxide SnO2The solution was spun uniformly onto the CYTOP uncovered ITO area on the sample at 3000rpm for 30s and annealed in a heated platen at 180 ℃ for 30 minutes. 9. Organic-inorganic hybrid infrared detection of perovskite (CH)3NH3)0.4(NH2CHNH2)0.6Sn0.6Pb0.4I3Preparation of the layer
(1) Configuration of infrared detection perovskite precursor liquid
Preparing the methylamine-plumbum-iodide-perovskite CH with the concentration of 1.25mol/L3NH3PbI3And methomyl stanniocalcitanite NH2CHNH2SnI3Stirring the solution for 12 hours at normal temperature, and mixing CH according to the volume ratio of 2:3 after uniformly stirring3NH3PbI3And NH2CHNH2SnI3The solution was stirred at room temperature for 12 hours.
(2) Graphical organic-inorganic hybrid infrared detection perovskite methylaminomethylether tin lead iodoperovskite (CH)3NH3)0.4(NH2CHNH2)0.6Sn0.6Pb0.4I3Preparation of the layer
Uniformly spin-coating and adsorbing the uniformly mixed organic-inorganic hybrid infrared detection perovskite precursor solution on a substrate at the rotation speed of 4000rpm, dropwise adding an anti-solvent in the rotated 7 th s, spin-coating for 30s, annealing for 20 minutes at the temperature of 100 ℃ in a heating table,obtaining the uniform and compact organic-inorganic hybrid infrared detection perovskite (CH) with the thickness of 500nm to 700nm3NH3)0.4(NH2CHNH2)0.6Sn0.6Pb0.4I3And (3) a layer.
9. Preparation of Polymer P3HT layer of Charge transport layer 3-hexylthiophene
(1) Preparation of Polymer P3HT solution of 3-hexylthiophene
1mL of chlorobenzene solution was added to 20mg of polymer P3HT of 3-hexylthiophene, and the mixture was allowed to stand for 12 hours to be sufficiently dissolved.
(2) Charge transport layer tin oxide SnO2Preparation of the layer
The fully dissolved polymer P3HT solution of 3-hexylthiophene is evenly coated on the surface of the organic-inorganic hybrid perovskite by spinning at 2000rpm for 40s, and is annealed for 10 minutes at 100 ℃ in a heating table.
10. Preparation of organic-inorganic hybrid perovskite photodiode metal Au electrode
Putting the substrate pasted with the metal electrode mask plate into an evaporation machine, and when the vacuum in the cavity of the evaporation machine reaches 9.9 multiplied by 10-4Passing a current through the metal Au boat at Pa
2nm, then opening a sample baffle to evaporate a 100nm gold electrode.
The experimental effect is as follows: and carrying out performance test on the novel perovskite infrared pixel unit by using a semiconductor analyzer.
As shown in fig. 11, the perovskite infrared pixel unit proposed for the application example of the present invention has a transfer characteristic curve under a dark condition. 0.1V is additionally arranged at the two ends of the source and the drain, and the on-state current of the transistor is 2.45 multiplied by 10 when no light is emitted-7A, at a light intensity of 685.5.5mW/cm2And the on-state current of the transistor under the irradiation of the light source with the wavelength of 940nm is increased to 5.175 x 10-6A; in the on state, the ratio of light to dark current was 21.1.
In summary, a patterned organic-inorganic hybrid infrared detection perovskite (CH) is deposited on an IGZO transistor3NH3)0.4(NH2CHNH2)0.6Sn0.6Pb0.4I3The layer greatly improves the absorption of the detector on infrared light wave bands, adopts a pixel unit structure formed by connecting an organic-inorganic hybrid perovskite photodiode and a metal oxide thin film transistor in series, takes full fluororesin CYTOP as a hydrophobic layer, and carries out graphical treatment on the hydrophobic layer, so that the hydrophobic layer covers the substrate and the rest parts of the device except an ITO electrode led out from the drain end of the metal oxide semiconductor thin film transistor, and tin oxide SnO2As a pattern electron transport layer, a spin coating adsorption method is used, and organic and inorganic hybrid infrared detection perovskite (CH) is formed after annealing3NH3)0.4(NH2CHNH2)0.6Sn0.6Pb0.4I3The layer adopts a polymer P3HT of 3-hexylthiophene as a hole transport layer material, and finally uses gold as an organic-inorganic hybrid perovskite photodiode metal electrode. The method avoids IGZO characteristic deterioration caused by the fact that ions in the perovskite enter the IGZO layer, and meanwhile effectively inhibits the defect of large dark current caused by the fact that the perovskite thin film in the spin-coating method is in direct contact with the metal source drain electrode.
It should be understood that the specific order or hierarchy of steps in the processes disclosed is an example of exemplary approaches. Based upon design preferences, it is understood that the specific order or hierarchy of steps in the processes may be rearranged without departing from the scope of the present disclosure. The accompanying method claims present elements of the various steps in a sample order, and are not intended to be limited to the specific order or hierarchy presented.
In the foregoing detailed description, various features are grouped together in a single embodiment for the purpose of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claimed embodiments of the subject matter require more features than are expressly recited in each claim. Rather, as the following claims reflect, invention lies in less than all features of a single disclosed embodiment. Thus, the following claims are hereby expressly incorporated into the detailed description, with each claim standing on its own as a separate preferred embodiment of the invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. To those skilled in the art; various modifications to these embodiments will be readily apparent, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the disclosure. Thus, the present disclosure is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
What has been described above includes examples of one or more embodiments. It is, of course, not possible to describe every conceivable combination of components or methodologies for purposes of describing the aforementioned embodiments, but one of ordinary skill in the art may recognize that many further combinations and permutations of various embodiments are possible. Accordingly, the embodiments described herein are intended to embrace all such alterations, modifications and variations that fall within the scope of the appended claims. Furthermore, to the extent that the term "includes" is used in either the detailed description or the claims, such term is intended to be inclusive in a manner similar to the term "comprising" as "comprising" is interpreted when employed as a transitional word in a claim. Furthermore, any use of the term "or" in the specification of the claims is intended to mean a "non-exclusive or".
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and it should be understood that the above-mentioned embodiments are merely exemplary embodiments of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. The photosensitive pixel unit of the perovskite image sensor is characterized by comprising a metal oxide thin film transistor and an organic-inorganic hybrid perovskite photodiode, wherein the metal oxide thin film transistor comprises a base substrate (1), a grid metal electrode (2), a grid insulating layer (3), a metal oxide semiconductor thin film (4), a source drain metal electrode (5), a silicon dioxide protective layer (6) and a hydrophobic layer thin film (7), and the organic-inorganic hybrid perovskite photodiode comprises an Indium Tin Oxide (ITO) electrode (8), a graphic electron transmission layer (9), an organic-inorganic hybrid perovskite material layer (10), a charge transmission layer (11) and a metal electrode (12); wherein, the grid metal electrode (2) is positioned on the basic substrate (1), the grid insulating layer (3) is positioned on the basic substrate (1) and wraps the grid metal electrode (2), the metal oxide semiconductor film (4), the Indium Tin Oxide (ITO) electrode (8), the source drain metal electrode (5) and the silicon dioxide protective layer (6) are positioned on the grid insulating layer (3), wherein the bottom parts of the source and drain metal electrodes (5) and the metal oxide semiconductor film (4) are positioned on the same plane, the source and drain metal electrodes (5) are partially covered on the metal oxide semiconductor film (4), the pattern electronic transmission layer (9) is positioned on the Indium Tin Oxide (ITO) electrode (8), and the silicon dioxide protective layer (6) wraps the metal oxide semiconductor film (4), the source drain metal electrode (5), the Indium Tin Oxide (ITO) electrode (8) and the pattern electronic transmission layer (9); the hydrophobic layer film (7) is positioned on the silicon dioxide protective layer (6), the organic-inorganic hybrid perovskite material layer (10) is positioned on the pattern electron transmission layer (9), the bottom area of the organic-inorganic hybrid perovskite material layer (10) is equal to that of the pattern electron transmission layer (9), the charge transmission layer (11) is positioned on the organic-inorganic hybrid perovskite material layer (10), the bottom area of the charge transmission layer (11) is equal to that of the organic-inorganic hybrid perovskite material layer (10), the metal electrode (12) partially covers the charge transmission layer (11), and the bottom area of the metal electrode (12) is smaller than the top area of the charge transmission layer (11); the silicon dioxide protective layer (6) partially wraps the organic-inorganic hybrid perovskite material layer (10), the hydrophobic layer film (7) wraps the charge transmission layer (11), and the metal electrode (12) is exposed outside the hydrophobic layer film (7).
2. The photosensitive pixel cell of the perovskite image sensor as claimed in claim 1, wherein the base substrate (1) is made of: glass, polyimide PI, polyethylene terephthalate PET or polyethylene naphthalate PEN.
3. The photosensitive pixel cell of perovskite image sensor according to claim 1, characterized in that the top surface of the organic-inorganic hybrid perovskite material layer (10) is higher than the top surface of the silicon dioxide protective layer (6), and the top surface of the charge transport layer (11) is lower than the top surface of the hydrophobic layer thin film (7).
4. The photosensitive pixel cell of the perovskite image sensor as claimed in claim 1, wherein the source drain metal electrode (5) and the metal oxide semiconductor thin film (4) are on the same plane; the grid metal electrode (2) is completely covered by the grid insulating layer (3), and the metal oxide semiconductor film (4) is deposited on the surface of the grid insulating layer (3).
5. The photosensitive pixel cell of the perovskite image sensor of claim 1,
the material of the hydrophobic layer film (7) comprises: perfluororesin CYTOP;
the material of the graphic electron transport layer (9) comprises: tin oxide SnO2Titanium oxide TiO2；
The thickness of the pattern electron transmission layer (9) is 10nm to 90 nm;
the patterned organic-inorganic hybrid perovskite material layer (10) is positioned right above the patterned electron transmission layer (9), and the projection area is equal to the exposed area of the hydrophobic layer thin film (7);
the chemical formula of the material of the patterned organic-inorganic hybrid perovskite material layer (10) is ABX3A comprises ABX3A includes methylamine ion CH3NH3 +Formamidine ion NH2CHNH2 +Cesium ion CS+Rb ion (Rb)+And a mixture formed by mixing the cations, wherein B comprises lead ions Pb2+Sn ion Sn2+Bismuth, bismuthIon Bi2+Europium ion Eu2+And a mixture formed by mixing the cations, wherein the tin ions are Sn2+Is an essential element, and the proportion of tin ions in B site cation elements is between 40 and 60 percent; x comprises I-、Cl-Or Br-(ii) a The perovskite has a light absorption capacity of 300nm to 1100 nm;
the thickness of the graphical organic-inorganic hybrid perovskite material layer (10) is 20nm to 2 um;
the material of the charge transport layer (11) comprises: polymer of 3-hexylthiophene P3HT, 2,7, 7-tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9, 9-spirobifluorene Spiro-MeOTAD, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] PTAA;
the thickness of the charge transport layer (11) is 10nm to 90 nm;
the material of the metal electrode (12) comprises: gold, silver, copper;
the material of the metal oxide semiconductor thin film (4) comprises: indium gallium zinc oxide IGZO, indium zinc tin oxide IZTO, aluminum-doped zinc oxide AZO, zinc tin oxide ZTO, magnesium zinc oxide MZO;
the thickness of the metal oxide semiconductor film (4) is 10nm to 100 nm;
the material of the silicon dioxide protective layer (6) comprises: polymethyl methacrylate PMMA, perfluoro resin CYTOP, silicon oxide SiOxSilicon nitride SiNxAnd alumina Al2O3；
The thickness of the silicon dioxide protective layer is 20nm to 900 nm.
6. The photosensitive pixel cell of the perovskite image sensor of claim 1,
the grid metal electrode (2) and the source drain metal electrode (5) are molybdenum, gold, silver, aluminum and copper material electrodes;
the grid metal electrode (2) and the source drain metal electrode (5) are in a strip block shape or an interdigital block shape;
the thickness of the grid metal electrode (2) and the thickness of the source drain metal electrode (5) are 30nm to 200 nm;
the length of a channel formed by the source drain metal electrode (5) is 1um to 100um, and the width is 1um to 1000 um; the gate insulating layer (3) is silicon oxide SiOxSilicon nitride SiNxAluminum oxide Al2O3Hafnium oxide HfO2A material;
the thickness of the gate insulating layer (3) is 50nm to 500 nm.
7. A method of manufacturing a photosensitive pixel cell of a perovskite image sensor as claimed in any of the claims 1 to 6, characterized by depositing a gate metal electrode (2) and a gate insulating layer (3) on the base substrate, the gate insulating layer (3) completely covering the gate metal electrode (2);
depositing a metal oxide semiconductor film (4) and a source drain metal electrode (5) on the gate insulating layer (3), wherein the source drain metal electrode (5) partially covers the metal oxide semiconductor film (4) and leaks out of the metal oxide semiconductor at the channel part;
the hydrophobic layer film (7) covers the entire except the organic-inorganic hybrid perovskite photodiode;
the pattern electron transmission layer (9), the organic-inorganic hybrid perovskite material layer (10), the charge transmission layer (11) and the perovskite photodiode metal electrode (12) are arranged on the indium tin oxide ITO electrode (8) which is not covered by the hydrophobic layer film (7), or the area of the perovskite photodiode metal electrode (12) is slightly smaller than the indium tin oxide ITO electrode (8) which is not covered by the hydrophobic layer film (7).
8. The method of fabricating a photosensitive pixel cell of a perovskite image sensor as claimed in claim 7,
-depositing a gate metal electrode (2) on said base substrate (1);
depositing a gate insulating layer (3) on the gate metal electrode (2).
9. The method of fabricating a photosensitive pixel cell of a perovskite image sensor as claimed in claim 8,
growing the grid metal electrode (2) on a basic substrate (1) by adopting a magnetron sputtering method or a vacuum evaporation method, and then forming a grid pattern by a photoetching process;
growing the grid insulation layer (3) on the grid metal electrode (2) by adopting a magnetron sputtering method or a chemical vapor deposition method;
directly growing the metal oxide semiconductor film (4) on the gate insulating layer (3) by adopting a magnetron sputtering method or a solution processing method, and then forming a block active region pattern by a photoetching process; annealing the device in an oxygen atmosphere, a nitrogen atmosphere or an air atmosphere at the temperature of 100-450 ℃ for 0.5-4 hours;
and directly growing the source and drain metal electrodes (5) on a base substrate by adopting a magnetron sputtering method or a vacuum evaporation method, and then forming a source and drain metal electrode pattern by a photoetching process, wherein the active region of the metal oxide semiconductor film (4) and the source and drain metal electrodes (5) are overlapped to a certain extent.
10. The method of fabricating a photosensitive pixel cell of a perovskite image sensor as claimed in claim 7,
preparing a hydrophobic layer film (7) except for the perovskite photodiode by using a solution processing method and a photolithography process or a plasma etching method; preparing a pattern electron transmission layer (9) on an Indium Tin Oxide (ITO) electrode (8) which is not covered by the hydrophobic layer film (7) by using a solution processing method; preparing a graphical organic-inorganic hybrid perovskite material layer (10) on the graphical electronic transmission layer (9) by adopting a solution spin coating method, a blade coating method, a spraying method, a vacuum evaporation method, a chemical vapor deposition method, a screen printing method or a roll-to-roll printing method, wherein the projection area of the graphical organic-inorganic hybrid perovskite material layer (10) is not more than the area of the Indium Tin Oxide (ITO) electrode (8); preparing a charge transport layer (11) on the organic-inorganic hybrid perovskite material layer (10) by a solution spin coating method, wherein the charge transport layer (11) completely covers the pattern electron transport layer (9) and the organic-inorganic hybrid perovskite material layer (10), and manufacturing the metal electrode (12) by a magnetron sputtering method or a vacuum evaporation method, wherein the projection area of the metal electrode (12) is equal to or smaller than the area of the charge transport layer (11).
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