CN114481054A - Oxide semiconductor target, thin film transistor and method for improving stability of oxide semiconductor target - Google Patents
Oxide semiconductor target, thin film transistor and method for improving stability of oxide semiconductor target Download PDFInfo
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- CN114481054A CN114481054A CN202210102412.0A CN202210102412A CN114481054A CN 114481054 A CN114481054 A CN 114481054A CN 202210102412 A CN202210102412 A CN 202210102412A CN 114481054 A CN114481054 A CN 114481054A
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- oxide semiconductor
- thin film
- ions
- film transistor
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/3407—Cathode assembly for sputtering apparatus, e.g. Target
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C23C14/3414—Metallurgical or chemical aspects of target preparation, e.g. casting, powder metallurgy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/02—Semiconductor bodies ; Multistep manufacturing processes therefor
- H01L29/12—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed
- H01L29/24—Semiconductor bodies ; Multistep manufacturing processes therefor characterised by the materials of which they are formed including, apart from doping materials or other impurities, only semiconductor materials not provided for in groups H01L29/16, H01L29/18, H01L29/20, H01L29/22
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L29/00—Semiconductor devices specially adapted for rectifying, amplifying, oscillating or switching and having potential barriers; Capacitors or resistors having potential barriers, e.g. a PN-junction depletion layer or carrier concentration layer; Details of semiconductor bodies or of electrodes thereof ; Multistep manufacturing processes therefor
- H01L29/66—Types of semiconductor device ; Multistep manufacturing processes therefor
- H01L29/68—Types of semiconductor device ; Multistep manufacturing processes therefor controllable by only the electric current supplied, or only the electric potential applied, to an electrode which does not carry the current to be rectified, amplified or switched
- H01L29/76—Unipolar devices, e.g. field effect transistors
- H01L29/772—Field effect transistors
- H01L29/78—Field effect transistors with field effect produced by an insulated gate
- H01L29/786—Thin film transistors, i.e. transistors with a channel being at least partly a thin film
- H01L29/7869—Thin film transistors, i.e. transistors with a channel being at least partly a thin film having a semiconductor body comprising an oxide semiconductor material, e.g. zinc oxide, copper aluminium oxide, cadmium stannate
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- Chemical & Material Sciences (AREA)
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- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Ceramic Engineering (AREA)
- Computer Hardware Design (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Thin Film Transistor (AREA)
- Physical Vapour Deposition (AREA)
Abstract
An oxide semiconductor target, a thin film transistor and a method for improving the stability and mobility of the thin film transistor are provided. And preparing a thin film material serving as a channel layer of the thin film transistor by using an oxide semiconductor target containing positive tetravalent lanthanide ions, and correspondingly preparing the thin film transistor. During illumination and negative grid voltage, the positive quadrivalent lanthanide series ion orbital hybrid transition absorbs blue light and even red and green light, and further down-converts the blue light and even the red and green light into low-energy light or a non-radiation form, so that the problems of increased conductivity and negative drift of threshold voltage caused by ionization of oxygen vacancies by blue light in backlight or self-luminescence are avoided, and the stability of NBIS is improved.
Description
Technical Field
The invention belongs to the field of semiconductor materials and devices, and particularly relates to an oxide semiconductor target, a thin film transistor using the oxide semiconductor thin film as a channel layer, and a method for improving the stability and the mobility of the thin film transistor.
Background
In recent years, Thin-Film transistors (TFTs) based on oxide semiconductors have been increasingly gaining attention in the field of flat panel displays, particularly organic electroluminescent displays (OLEDs).
TFTs, which are core components of display devices, are inevitably exposed to light in applications in the display field. For example: in liquid crystal display, the channel of the thin film transistor is irradiated by backlight; in OLED display, the channel of the thin film transistor is affected by self-luminescence of the OLED. Whether the backlight source or the OLED is self-luminous, the light emission is in a visible light range, and the largest photon energy is blue light emission. Oxide semiconductors (such as IZO and IGZO) are particularly sensitive to blue light because blue light ionizes oxygen vacancies of the oxide semiconductors and releases electrons into a conduction band to participate in conduction, thereby negatively drifting the threshold voltage of oxide semiconductor-based TFTs (referred to as oxide TFTs) and causing deterioration of display images.
Oxide semiconductor with neutral oxygen vacancy (V) under blue light irradiationO) Ionization to form positive divalent oxygen vacancy (V)O 2+) Can cause lattice relaxation (e.g., V of ZnO)OThere will be 12% inward relaxation, and V after ionizationO 2+There is 23% outward relaxation, with volume change before and after ionization up to 35%), so its ionization and recovery processes are slow, causing the threshold voltage to drift continuously. Especially under negative gate bias and illumination, the energy band at the interface is tilted up and the valence band top is closer to the Fermi level, resulting in VO 2+The generation Energy (Formation Energy) of (V) is greatly reduced, in which case V is set to be substantially lower than in the case of the Formation Energy of (V)OWill ionize more easily under light to form VO 2+Meanwhile, a large amount of photo-generated electrons are formed, and the threshold voltage drift phenomenon is serious. Therefore, not only the stability of the oxide TFT under the influence of light is improved, but also the problem of the stability of the threshold voltage of the oxide TFT under the influence of light plus Negative gate bias stress (NBIS) needs to be solved.
In the prior art, by adding a black matrix, light shielding treatment is performed on a channel layer of a thin film transistor, so that light stability can be improved to a certain extent. However, this method merely solves the problem of stability under the influence of light irradiation, cannot solve the problem of light entering the oxide semiconductor layer by diffraction, and has a limited improvement in stability under long-term light irradiation conditions; moreover, the light shielding process is added, that is, the complexity of the preparation is increased, resulting in an increase in the manufacturing cost. Therefore, it is very important to improve the light stability of the oxide semiconductor itself.
Patent document 1(CN201710229199.9) discloses a rare earth oxide-doped oxide semiconductor thin film doped with praseodymium oxide, terbium oxide, dysprosium oxide, or ytterbium oxide. In the oxide doped in this patent, the rare earth element is trivalent, for example, praseodymium oxide is praseodymium trioxide, terbium oxide is also terbium trioxide, dysprosium oxide is dysprosium trioxide, and ytterbium oxide is ytterbium trioxide. According to the description of patent document 1, the principle of doping praseodymium oxide, terbium oxide, dysprosium oxide or ytterbium oxide is that praseodymium, terbium oxide, dysprosium oxide and ytterbium atom replaces original metal atom to weaken the original M-M interaction, so that valence band top displacement is caused, and the energy band structure of the original oxide semiconductor material is converted from a direct band gap to an indirect band gap. When incident light irradiates, valence band electrons of the indirect band gap need to interact with phonons to jump to a conduction band, so that contribution is made to transport characteristics, and the difficulty of increasing the generation of photo-generated electrons is increased. The material can reduce the threshold voltage shift of the device when the thin film transistor is irradiated by incident light, namely, the stability of illumination (without negative gate bias) is improved. However, the method of changing the band (valence band top) structure by doping rare earth elements and increasing the difficulty of generating photo-generated electrons can only improve the stability of illumination (without adding negative gate bias), and cannot fundamentally solve the problem of poor stability under more important illumination plus negative gate bias stress (NBIS) faced by oxide TFTs. Because under negative gate bias, the energy band bends, the valence band at the interface warps upwards, the distance between the valence band top and the Fermi level is shortened, and oxygen vacancies (V) in positive and divalent states are generatedO 2+) The generated energy is greatly reduced; in this case, neutral oxygen vacancy (V) is formed under irradiation with lightO) More easily ionized, resulting in negative drift of the NBIS lower threshold voltage. That is, the method of reference 1 has much smaller effect on the change of the valence band top than the negative gate bias; therefore, the stability under illumination (without negative gate bias) can only be improved, and the more important illumination plus negative gate bias stress (NBIS) faced by oxide TFT cannot be fundamentally solvedAnd (4) a poor problem.
Non-patent document 1(ACS appl. mater. interfaces 2019,11,5232-5239) and non-patent document 2(phys. status Solidi a 2021,218,2000812) disclose a Pr-doped oxide semiconductor material which, as an intermediary, can accelerate the recombination of electrons with positive divalent oxygen vacancies, reduce the lifetime of photogenerated electrons generated by oxygen vacancy ionization, and improve the stability of light irradiation (without applying a negative gate bias). However, ionization of neutral oxygen vacancy is not prevented in the mode, and Pr electrons are newly introduced to serve as electron traps, so that the electron traps can capture photo-generated electrons, and can also capture or scatter normal carriers, so that the mobility is reduced; meanwhile, because ionization of oxygen vacancies is not prevented, only recombination is accelerated, and rapid relaxation of crystal lattices is caused, under illumination plus negative bias stress (NBIS), because a large number of oxygen vacancies are ionized, the overall relaxation (expansion) of the crystal lattices is large, and the crystal lattices cannot be rapidly recovered, the method can only improve the stability of illumination (without adding negative gate bias) and cannot thoroughly improve the stability under the illumination plus negative gate bias stress (NBIS). In addition, both the positive trivalent (containing 2 f electrons) and the positive quadrivalent (containing 1 f electron) contain less than full (or less than half full) f electrons, and the less than full or less than half full f electron structure is unstable and can be seriously influenced by a crystal field to form cleavage, so that a large number of defect state energy levels are caused, and the mobility and the subthreshold swing are seriously influenced. Therefore, in the oxide semiconductor material, the introduction of Pr ions cannot improve both the mobility and NBIS stability.
Patent document 2(CN202011511468.9) discloses an oxide semiconductor doped with a trivalent positive rare earth compound, in which the absorption of the f-d transition is red-shifted by adjusting the electronegativity of an anion. However, decreasing the electronegativity of the anion decreases the binding energy of the rare earth ion and the anion, so that impurities are decomposed to form during high-temperature sintering, thereby affecting the improvement of the performance.
Therefore, it is necessary to provide a solution that can essentially solve the stability problem of TFT devices under illumination plus negative gate voltage stress (NBIS), and that does not introduce new impurities or defect levels causing mobility degradation or process complexity increase.
Disclosure of Invention
The invention aims to solve the NBIS stability problem of the oxide TFT device essentially, realize good device stability of the oxide TFT under illumination, particularly under NBIS, and avoid the additional performance, particularly the mobility, deterioration caused by the complexity of the preparation process or the introduction of other impurities (or defect energy levels) due to a new scheme.
The above object of the present invention is achieved by the following technical means:
an oxide semiconductor target is provided, which comprises a matrix oxide semiconductor material and a positive quadrivalent lanthanide ion, wherein the matrix oxide semiconductor material contains at least one of In, Zn, Sn, Ga and Cd.
The stable valence state of the lanthanide ion in the lanthanide oxide is usually trivalent and trivalent, such as lanthanum oxide, praseodymium oxide, neodymium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, etc. are usually sesquioxide (Ln)2O3) Only cerium oxide may be present in the form of CeO2The form (2) exists stably. The f-d transition of the positive trivalent lanthanide ion is wide spectrum absorption, but the f-d transition energy gap of the positive trivalent rare earth ion is large, so that the positive trivalent lanthanide ion only has strong wide spectrum absorption to ultraviolet or purple light generally, and cannot absorb a large amount of blue light, and therefore, the problem of long-time threshold voltage stability under negative bias and visible light (LED backlight) irradiation (NBIS) cannot be solved. Ce3+The f-d absorption edge of the trivalent ion is the lowest and is positioned in the purple light region, and the f-d absorption edges of other trivalent ions are positioned in the ultraviolet light region. Tb3+The f-d transition of (a) requires a relatively high energy and the transition cannot be achieved by absorbing blue light, and thus, Tb3+The broad spectrum of intense light emitted by the LED (blue portion) cannot be absorbed. Praseodymium (Pr) in the trivalent state3+) Has weak band-shaped absorption in the blue light region of 450nm, which is Pr3+The f-f transition of (a) is absorbed, but the absorption is weaker because the f-f belongs to forbidden transition; in addition, the molar extinction absorption coefficient of the f-f transition is small, and the f-f transition absorption belongs to narrow spectrum absorption, and cannot completely absorb the light (blue light part) with wide spectrum and strong intensity emitted by the LED. Therefore, doping with trivalent lanthanide ions has limited effect on improving photostability.
Part of lanthanide ions can have positive quadrivalence or positive bivalence under special conditions, and lanthanide ions with different valence states have channel hybridization charge transition absorption. In the process of positive tetravalent lanthanide ion orbital hybridization transition, the charge transition can absorb blue light or visible light, and the relaxation of cations and anions can be mostly counteracted during orbital hybridization charge transition, so that large overall relaxation cannot be caused, therefore, the orbital hybridization charge transition of lanthanide ions is easier to absorb photons than oxygen vacancies (the oxygen vacancies are inhibited from absorbing photons), and rapidly returns to the ground state through radiationless transition and the like. The problem that ionization process and recovery process are slow due to severe lattice relaxation (expansion) caused by oxygen vacancy ionization is solved, and continuous threshold voltage drift is avoided.
Preferably, in the oxide semiconductor target, the positive tetravalent lanthanide ion is Tb4+。
Preferably, the oxide semiconductor target material, Tb4+Ion number and Tb3+The ratio of the number of ions is greater than 0.1.
Preferably, the oxide semiconductor target material, Tb4+Ion number and Tb3+The ratio of the number of ions is greater than 1.
More preferably, the oxide semiconductor target material, Tb4+Ion number and Tb3+The number of ions is greater than 2.
Most preferably, the oxide semiconductor target contains only Tb4+Does not contain Tb3+I.e. the matrix oxide semiconductor material is doped with positive quadrivalent terbium ion Tb only4+。
In the prior art, the target needs to be sintered at high temperature, and even if the positive quadrivalent lanthanide ions exist in the raw materials, the lanthanide ions are easy to deoxidize and be reduced to positive trivalent ions in the high-temperature sintering process of the target due to the low redox potential. Thus, it is difficult to effectively incorporate a tetravalent lanthanide ion into the host oxide semiconductor material, with the lanthanide ion being substantially trivalent and trivalent in practical conventional target compositions. Solution processes can form positive tetravalent lanthanide ions in special cases, but the precursors and solvents introduce large amounts of impurities, thereby reducing mobility. Oxide powder of lanthanide ions generally has a normal stable structure, and it is difficult to directly oxidize it into positive tetravalent oxide powder by a common method. In the field of conventional oxide semiconductor targets, targets containing positive tetravalent lanthanide ions are not common, so that the technical scheme of the oxide semiconductor target containing the positive tetravalent lanthanide ions cannot be technically arranged. Or, the person skilled in the art would not want to think in this direction. The method overcomes the technical prejudice, and selects the oxide semiconductor target material containing the positive quadrivalent lanthanide ions as the technical scheme of the invention.
Further, the oxide semiconductor target is prepared by the following method: firstly, oxide powder of lanthanide and matrix oxide semiconductor material powder are uniformly mixed, then are sintered in a strong oxidizing atmosphere, are subjected to cold isostatic pressing or hot press molding after being subjected to secondary grinding and mixing, and are sintered in the strong oxidizing atmosphere to obtain the oxide semiconductor target. According to the method, terbium oxide powder and matrix oxide semiconductor material powder are mixed and sintered for multiple times, and when lanthanide ions and matrix oxide semiconductor material form a solid solution phase, trivalent lanthanide ions are easily oxidized into tetravalent lanthanide ions, so that the technical problem that tetravalent lanthanide ions are easily deoxidized to reduce trivalent positive ions and tetravalent positive lanthanide ions are not easily obtained when a target is sintered by a common method in the prior art is solved, and the proportion of tetravalent lanthanide ions in the target can be improved. It should be noted that the target material of the present invention is not limited to the preparation by this method.
The invention breaks through the limit that the target material made of the conventional lanthanide elements is trivalent, and sets a new method for setting the oxide semiconductor target material containing the positive quadrivalent lanthanide ions, particularly Tb4+The technical scheme of (1). Formation of a semiconductor material having positive tetravalent Tb using a host oxide semiconductor material4+For preparing a channel layer as a thin film transistor. Due to positive quadrivalence Tb4+The energy required by the track hybridization transition is low, when the thin film transistor is illuminated, the thin film transistor can absorb blue light and even red and green light, and further down-convert the blue light and even red and green light into a non-radiative form, thereby avoiding backlight or self-luminescenceThe blue light ionizes oxygen vacancies to cause the problems of increased conductance and negative drift of threshold voltage, thereby improving the illumination stability of the device; under the condition of illumination and negative grid voltage stress (NBIS), the problem of negative drift of the threshold voltage of the device can be solved; the problem of complicated preparation process is avoided, impurities or crystal field splitting energy level defects are not introduced, electron transport is not influenced, and the TFT device with good NBIS stability and high mobility is realized.
The invention also provides an oxide semiconductor film which is prepared by a physical vapor deposition method, the thickness of the oxide semiconductor film is 3-200nm, and the target material used by the physical vapor deposition is the oxide semiconductor target material.
The present invention also provides a method of improving the stability of a thin film transistor,
preparing an oxide semiconductor target material, wherein the semiconductor target material comprises a matrix oxide semiconductor material and positive tetravalent lanthanide ions serving as functional ions, the functional ions can perform orbital hybridization, the energy required by orbital hybridization transition is not higher than that of blue light, and the functional ions are converted into a non-radiative form after orbital hybridization transition;
depositing an oxide semiconductor thin film for use as a channel layer of a thin film transistor through the oxide semiconductor target;
when the thin film transistor has illumination or illumination and negative grid bias voltage, the functional ions absorb blue light and even red and green light to realize orbital hybrid transition and convert the blue light and the red and green light into a non-radiative form; and the ionization of oxygen vacancies is prevented by absorbing illumination through the hybridization transition of functional ion orbitals, so that the serious lattice relaxation is avoided, and the threshold voltage drift is avoided.
Further, in the above method for improving stability and mobility of the thin film transistor, the positive tetravalent lanthanide ion is Tb4 +，Tb4+Ion number and Tb3+The ratio of the number of ions is greater than 0.1.
Preferably, the method for improving the stability of the thin film transistor is to deposit the oxide semiconductor thin film by a physical vapor deposition method.
The invention also provides a thin film transistor provided with a gate electrode, a channel layer, an insulating layer, and the like, the channel layer comprising one or more oxide semiconductor layers, wherein at least one of the oxide semiconductor layers is provided as the above-described oxide semiconductor thin film.
The thin film transistor is used for a driving back plate of display, and can also be used for an internal memory, a flash memory and a dynamic random access memory.
Compared with the prior art, the invention has the following advantages and beneficial effects:
the invention uses the oxide semiconductor target containing positive quadrivalent lanthanide series ion, especially positive quadrivalent terbium ion, to prepare the film material as the film transistor channel layer, and prepare the film transistor. Because the energy required by the orbital hybridization transition of the positive tetravalent terbium ion is lower, when the thin film transistor is illuminated, blue light and even red and green light can be absorbed and further converted into a non-radiative form, the problems of conductivity increase and threshold voltage negative drift caused by ionization of oxygen vacancy by the blue light in a backlight source or self-luminescence are avoided, and the illumination stability of the device is improved; under the condition of illumination plus negative grid voltage stress (NBIS), the problem of negative drift of the threshold voltage of the device can be solved; the problem of complicated preparation process is avoided, impurities or crystal field splitting energy level defects are not introduced, electron transport is not influenced, and the TFT device with good NBIS stability and high mobility is realized.
Therefore, the oxide semiconductor target, the thin film and the transistor can keep the migration performance and improve the NBIS stability.
Drawings
In order to more clearly illustrate the technical solution of the present invention, the drawings needed to be used in some embodiments of the present invention will be briefly described below, and it is apparent that the drawings in the following description are only drawings of some embodiments of the present invention, and other drawings can be obtained by those skilled in the art according to the drawings. Furthermore, the drawings in the following description may be regarded as schematic diagrams, and do not limit the actual size of products, the actual flow of methods, the actual timing of signals, and the like according to the embodiments of the present invention.
FIG. 1 is a schematic structural diagram of a thin film transistor according to the present invention;
fig. 2 is a schematic diagram of an AMOLED display pixel driving, which takes an address selection transistor TFT1 and a driving transistor TFT2 as an example;
FIG. 3 is a schematic of the absorption energy levels of the f-d transition of a trivalent positive lanthanide ion in some experiments in accordance with the present invention.
FIG. 4 is a schematic representation of the lowest energy required for the hybridization charge transitions of the positive trivalent and positive quadrivalent lanthanide ion orbitals in some experiments of the invention.
FIG. 5 shows different Tb's in example 5 of the present invention4+Reflectance spectrum of doped amount of target material.
FIG. 6 shows In utilization In example 6 of the present invention2O3Incorporation of Tb4+/Tb3+The Tb 4p peak spectrum of X-ray photoelectron spectroscopy (XPS) of the film prepared by sputtering the target material with the ratio of (1/1).
FIG. 7 shows pure In example 6 of the present invention2O3Transfer characteristics under NBIS of thin film transistors without Tb incorporation.
FIG. 8 shows In example 6 of the present invention2O3Incorporation of 3% Tb, and Tb4+/Tb3+Transfer characteristics under NBIS of the thin film transistor in the case of 1/0.
FIG. 9 shows In example 6 of the present invention2O3Incorporating 3% Tb, and Tb4+/Tb3+Transfer characteristic curve under NBIS of thin film transistor in case of 1/1
Fig. 10 is a schematic structural diagram of a thin film transistor in embodiment 9 of the present invention.
FIG. 11 shows the reflectance spectra of targets with different amounts of Pr doping in example 10 of the present invention.
FIG. 12 shows a graph based on 3% Pr in example 11 of the present invention4+Transfer characteristics of the content of Thin Film Transistors (TFTs) under NBIS (white light illumination of the LED plus a gate bias of-20V).
FIG. 13 shows a graph based on 7% Pr in example 11 of the present invention4+Transfer characteristic curves for Thin Film Transistors (TFT) under NBIS (white light illumination of LED plus-20V gate bias).
FIG. 14 is an implementation of the present invention3% Pr-based in example 114+Content and same Tb4+The fluorescence spectra of the films in the contents were compared.
Detailed Description
The technical solutions in some embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is to be understood that the described embodiments are only a part of the embodiments of the present disclosure, and not all of the embodiments. The scope of the invention is not limited to the embodiments, and all other embodiments obtained by a person of ordinary skill in the art based on the embodiments provided by the present disclosure belong to the scope of the present disclosure.
Unless the context requires otherwise, throughout the description and the claims, the terms "comprise" (or include, contain, comprise) "and other forms thereof such as the third person's singular form" comprising "and the present participle form" comprising "are to be interpreted in an open, inclusive sense, i.e., as" including, but not limited to ". In the description of the specification, the terms "one embodiment", "some embodiments", "example", "specific example" or "some examples" and the like are intended to indicate that a particular feature, structure, material, or characteristic associated with the embodiment or example is included in at least one embodiment or example of the present disclosure. The schematic representations of the above terms are not necessarily referring to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be included in any suitable manner in any one or more embodiments or examples.
Herein, a host oxide semiconductor material (e.g., In)2O3、ZnO、InGaZnO4Etc.) may be perfectly stoichiometrically matched, or non-stoichiometrically matched conditions such as oxygen vacancies, oxygen interstitials, cation vacancies, cation interstices, etc. may exist.
As used herein, "ion" is a representation of a chemical valence state, and is not limited to ionic compounds, but rather, elements of ionic compounds and covalent compounds may be referred to as "ions".
"at least one of A, B and C" has the same meaning as "A, B or at least one of C", both including the following combination of A, B and C: a alone, B alone, C alone, a and B in combination, a and C in combination, B and C in combination, and A, B and C in combination.
"A and/or B" includes the following three combinations: a alone, B alone, and a combination of A and B.
The use of "adapted to" or "configured to" herein is meant to be an open and inclusive language that does not exclude devices adapted to or configured to perform additional tasks or steps.
Additionally, the use of "based on" means open and inclusive, as a process, step, calculation, or other action that is "based on" one or more stated conditions or values may in practice be based on additional conditions or values beyond those stated.
Example embodiments are described herein with reference to cross-sectional and/or plan views as idealized example figures. In the drawings, the thickness of layers and regions are exaggerated for clarity. Variations from the shapes of the illustrations as a result, for example, of manufacturing techniques and/or tolerances, are to be expected. Thus, the exemplary embodiments should not be construed as limited to the shapes of regions illustrated herein but are to include deviations in shapes that result, for example, from manufacturing. For example, an etched region shown as a rectangle will typically have curved features. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the actual shape of a region of a device and are not intended to limit the scope of the exemplary embodiments.
Some embodiments of the present disclosure provide a display device, which includes a display panel, and a driving circuit, such as a pixel driving circuit, a gate driving circuit, etc., disposed on the display panel.
Thin-Film transistors (TFTs) are important components constituting a pixel driving circuit, a gate driving circuit, and the like, and in the power-on process, the pixel driving circuit and the gate driving circuit can be controlled to drive the display panel for displaying by controlling the on and off of the TFTs. It should be noted that the thin film transistor is one of the transistors, and the material, the manufacturing method and the device of the present invention are applicable to all types of transistors, and are not limited to the thin film transistor; the application range is not limited to the display field, and other application fields of the transistor, such as a memory, a flash memory, a dynamic random access memory and the like, can also be included.
The Display device may be one of LCD (Liquid Crystal Display), OLED (Organic Light-Emitting Diode), QLED (Quantum Dot Light-Emitting Diode), Micro led (Micro Light-Emitting Diode), MiniLED (Mini Light-Emitting Diode), and the like.
The display device may be a mobile phone, a tablet computer, a notebook, a Personal Digital Assistant (PDA), a car computer, a laptop, a digital camera, etc.
The form of the display device is not limited, and rigid display, flexible display, stretchable display, display of any shape, and the like can be used.
The TFT mainly includes an amorphous silicon (e.g., hydrogenated amorphous silicon: a-Si: H) TFT, a Low Temperature Poly-silicon (LTPS) TFT, an oxide TFT, an organic TFT, and the like, depending on the material of the channel layer.
Wherein the oxide TFT is an oxide semiconductor (e.g. In)2O3ZnO, InZnO, InGaZnO, etc.) as a channel layer, much attention has been paid to the advantages of relatively high carrier mobility of an oxide semiconductor, low process temperature, low off-state current, good uniformity of devices, and the like. Meanwhile, the oxide TFT has some problems to be solved, for example, the stability of the oxide TFT under the negative gate voltage stress (NBIS) is still insufficient. Particularly, in the case of a TFT which is a display panel member, it is inevitably irradiated with light in the application to the display field. For example, as shown in FIG. 1, in a liquid crystal display, the channel 131 of the TFT may be illuminated by a backlight, and in an OLED display, the channel 131 of the TFT may be illuminated by a backlightTo OLED self-luminescence. Whether the backlight source or the self-luminous light source is adopted, the light emission is in a visible light range, and the light with the largest photon energy is blue light emission. Oxide semiconductors (such as IZO (Indium Zinc Oxide), IGZO (Indium Gallium Zinc Oxide), etc.) are particularly sensitive to blue light, because blue light ionizes oxygen vacancies in the Oxide semiconductor material and releases electrons into a conduction band to participate in conduction, thereby negatively drifting threshold voltage and causing deterioration of a display screen.
Here, as shown in fig. 2, in an AMOLED (Active-matrix organic light emitting diode) display pixel drive, at least two TFTs, which are called an address selection transistor TFT1 and a driving transistor TFT2, are included, and since most of the oxide TFTs only display n-channel characteristics, they are turned on at a positive gate voltage and turned off at a negative gate voltage (when the concentration of the oxide semiconductor carrier is high, a normally-on state occurs, that is, a negative gate voltage is required to turn off the oxide TFT completely). The address transistor TFT1 is turned on only once in each scan cycle, and is turned off during the rest of the scan cycle, so that the stability of the address transistor TFT1 under Negative Bias Stress (NBS) is very important. The source electrode of the driving transistor TFT2 is directly connected to the OLED, so that as long as the OLED emits light, a certain amount of current flows through the source and drain electrodes of the driving transistor TFT2, and therefore, the driving transistor TFT2 is basically in an on state, and stability under Positive gate Stress (PBS) is important, and the oxide TFT will show a threshold voltage (V) under gate Stressth) A drift phenomenon.
Hereinafter, the case of causing the threshold voltage shift under illumination will be described in detail. Neutral oxygen vacancy (V) under blue light irradiationO) Ionization to form positive divalent oxygen vacancy (V)O 2+) Can cause lattice relaxation (e.g., V of ZnO)OThere will be 12% inward relaxation, and V after ionizationO 2+There is 23% outward relaxation, with volume change before and after ionization up to 35%), so its ionization and recovery processes are slow, causing the threshold voltage to drift continuously. Especially under negative gate bias plus illumination,the energy band at the interface is tilted up and the valence band top is closer to the Fermi level, resulting in VO 2+The generation Energy (Formation Energy) of (V) is greatly reducedOWill ionize more easily under light to form VO 2+Meanwhile, a large amount of photo-generated electrons are formed, and the threshold voltage drift phenomenon is serious. Therefore, it is important to improve the threshold voltage stability of the oxide TFT under NBIS (Negative bias illumination stress).
Some embodiments of the present invention provide a transistor (or a thin film transistor) provided with a gate electrode, a channel layer provided as the above-described oxide semiconductor thin film including a host oxide semiconductor material and a positive tetravalent lanthanoid ion, an insulating layer, and the like. In some embodiments, the transistor comprises: the grid electrode, the channel layer, the insulating layer positioned between the grid electrode and the channel layer, and the source electrode and the drain electrode which are respectively and electrically connected with two ends of the channel layer; the electrical connection means that a conductive channel is arranged between the two, and the two can be in direct contact with each other, and can further comprise a buffer layer and the like. It is to be noted that the specific structure of the transistor may adopt different structure types such as a bottom gate top contact, a bottom gate bottom contact, a top gate top contact, a top gate bottom contact, and the like, as long as the channel layer thereof is the above-mentioned oxide semiconductor thin film containing the host oxide semiconductor material and the positive tetravalent lanthanoid ion, which belong to the technique of the present invention.
In some embodiments, the channel layer may comprise one or more thin films, wherein at least one of the thin films is provided as the oxide semiconductor thin film comprising a host oxide semiconductor material and a positive tetravalent lanthanide ion described above. At this time, the thin films at different positions of the channel layer can be made of oxide semiconductor materials doped with different positive tetravalent lanthanide ions; or the same positive quadrivalent lanthanide ion doping and different doping amount of oxide semiconductor material are selected; or any combination of thin films of oxide semiconductor material doped with positive tetravalent lanthanide ions and oxide semiconductor material not doped with positive tetravalent lanthanide ions. Here, the application position and the application doping ratio of the oxide semiconductor material doped with the positive tetravalent lanthanide ion in the channel layer are not particularly limited.
Hereinafter, the technical solution provided by the present invention will be exemplarily described in detail through specific experimental examples.
Example 1.
An oxide semiconductor target comprising a matrix oxide semiconductor material and a positive tetravalent lanthanide ion Tb4+. The matrix oxide semiconductor material is an oxide material and contains at least one of five elements including In, Zn, Sn, Ga and Cd.
The matrix oxide semiconductor material is an oxide material, contains at least one of five elements of In, Zn, Sn, Ga and Cd, and can further contain at least one of elements such as Al, B, Sc, Y, Zr, Hf, Ta, W and Mg.
The innovation point of the scheme is to form a target material containing positive quadrivalent lanthanide ions. The modifying substance being, in addition to the host oxide semiconductor material, a positive tetravalent lanthanide ion Tb4+Usually, Tb is contained in a certain proportion due to factors such as preparation process3+. Except for Tb4+、Tb3+In addition, other elemental substances are not treated as impurities for the target dopant substance, and ideally the target material does not contain impurities. The oxide semiconductor target material must contain a certain proportion of Tb4+Ions of other valency states, e.g. Tb3+Or other impurities are not required.
In the oxide semiconductor target material, the ratio of the number of terbium ions to the number of all cations is between 0.05% and 10%. It should be noted that, the ratio relationship between the substrate oxide semiconductor material and the modified substance in the target material can be flexibly selected by those skilled in the art according to actual needs, which is not a main research problem of the present invention.
In order to make the oxide semiconductor target material meet the required performance, Tb in the target material is controlled and improved4+The content of ions is critical. Specifically, in the oxide semiconductor target, Tb4+Ion number and Tb3+The ratio of the number of ions is controlled to 0.1 or more, preferably 1 or more, and more preferably 2 or more. Oxidation by oxygenIn the target material of the object semiconductor, the modified substance is Tb4+The performance is best.
In the prior art, an oxide semiconductor target containing positive quadrivalent lanthanide ions is difficult to obtain and almost does not exist. The lanthanide ion is represented by Ln, since Ln3+—Ln4+Has a low redox potential and is difficult to remove from In2O3、ZnO、SnO2Oxygen is deprived from the oxide semiconductor to be oxidized into positive quadrivalence; in addition, the positive quadrivalent lanthanide ions are easy to deoxidize and be reduced into positive trivalent ions in the high-temperature sintering process of the target material. Therefore, it is difficult to effectively incorporate a positive tetravalent lanthanide ion in the host oxide semiconductor material. Solution processes can form positive tetravalent lanthanide ions in special cases, but the precursors and solvents introduce impurities that reduce mobility. Oxide powder of lanthanide ions generally has a normal stable structure, and is difficult to be directly oxidized into positive tetravalent oxide powder by a common method; when the target is sintered at high temperature by a common method, the target is easy to deoxidize so that the positive quadrivalent lanthanide series ions are reduced into positive trivalent ions. The above factors limit the difficulty in obtaining oxide semiconductor targets containing positive quadrivalent lanthanide ions in the prior art. Thus, in the case where raw materials are not readily available, the skilled person would not consider the related art concept of improving the stability of thin film transistor NBIS by positive tetravalent lanthanide ions.
The invention breaks through the limitation that the target material made of the conventional lanthanide is trivalent, and overcomes the technical bias of setting a technical scheme that the oxide semiconductor target material contains positive quadrivalent lanthanide ions. The method of the invention utilizes a process to make tetravalent lanthanide ions and a matrix oxide semiconductor material form a solid solution phase, and the trivalent lanthanide ions are relatively easy to be further oxidized into tetravalent lanthanide ions, thereby improving the proportion of the tetravalent lanthanide ions in the target material.
The target material is prepared by the following method: the terbium oxide powder and the matrix oxide semiconductor material powder are uniformly mixed, then sintered in a strong oxidizing atmosphere, ground, mixed, formed by cold isostatic pressing or hot pressing, and sintered in the strong oxidizing atmosphere. The preparation method of the target material can be used for controllingIncrease Tb4+Ion number and Tb3+The ratio of the number of ions.
Specifically, terbium oxide powder and matrix oxide semiconductor material powder are uniformly mixed, then sintered in a strong oxidizing atmosphere, ground, mixed, formed by cold isostatic pressing or hot pressing, and then sintered in a strong oxidizing atmosphere. Or terbium oxide powder can be further oxidized into dioxide or into oxides of positive quadrivalent and positive trivalent lanthanide series ions or a mixture, the mixture is uniformly mixed with the matrix oxide semiconductor material powder after being ground, then the mixture is sintered in a strong oxidizing atmosphere, and the mixture is subjected to cold isostatic pressing or hot pressing molding after being ground and mixed for the second time and then the mixture is sintered in the strong oxidizing atmosphere. It should be noted that the oxide semiconductor target material of the present invention is not limited to being prepared by the preparation method in the present embodiment, and other preparation methods are also applicable to the preparation of the oxide semiconductor target material of the present invention.
The stable valence state of the lanthanide ion in the lanthanide oxide is usually trivalent and trivalent, such as lanthanum oxide, praseodymium oxide, neodymium oxide, gadolinium oxide, terbium oxide, dysprosium oxide, etc. are usually sesquioxide (Ln)2O3) Exist in the form of (1). The f-d transition of the positive trivalent lanthanide ion is wide spectrum absorption, but the f-d transition energy gap of the positive trivalent rare earth ion is large, so that the positive trivalent rare earth ion only has strong wide spectrum absorption for ultraviolet or purple light generally, and cannot absorb a large amount of blue light, so that the problem of long-time threshold voltage stability under negative bias and visible light (LED backlight) irradiation (NBIS) cannot be solved. FIG. 3 shows the absorption edge of the f-d transition of a trivalent lanthanide cation, and it can be seen that Ce3+The f-d absorption edge of the trivalent ion is the lowest and is positioned in the purple light region, and the f-d absorption edges of other trivalent ions are positioned in the ultraviolet light region. Tb3+The f-d transition of (a) requires a relatively high energy and the transition cannot be achieved by absorbing blue light, and thus, Tb3+The broad spectrum of intense light emitted by the LED (blue portion) cannot be absorbed. Praseodymium (Pr) in the trivalent state3+) Has weak band-shaped absorption in the blue light region of 450nm, which is Pr3+The f-f transition of (a) is absorbed, but the absorption is weaker because the f-f belongs to forbidden transition; in addition, the molar extinction absorption coefficient of the f-f transition is small, and the f-f transition is absorbedThe absorption is narrow spectrum absorption and cannot completely absorb the broad spectrum intense light (blue light part) emitted by the LED. Therefore, doping with trivalent lanthanide ions has limited effect on improving photostability.
The lanthanide ions are mainly stable in valence states of positive trivalent, part of the lanthanide ions can have positive quadrivalent, and lanthanide ions in different valence states have channel hybrid charge transition absorption. In the process of positive tetravalent lanthanide ion orbital hybridization transition, the charge transition can absorb blue light or visible light, and the relaxation of cations and anions can be mostly counteracted during orbital hybridization charge transition, so that large overall relaxation cannot be caused, therefore, the orbital hybridization charge transition of lanthanide ions is easier to absorb photons than oxygen vacancies (the oxygen vacancies are inhibited from absorbing photons), and rapidly returns to the ground state through radiationless transition and the like. The problem that ionization process and recovery process are slow due to serious lattice relaxation (expansion) caused by oxygen vacancy ionization is solved, and continuous drift of threshold voltage is avoided.
FIG. 4 shows the lowest energy (absorption edge) required for the orbital hybrid charge transition of trivalent and tetravalent lanthanide ions in some experiments, and it can be seen that the absorption edges of trivalent lanthanide ions are both greater than 4.5eV and are in the UV region. Compared with f-f transition and f-d transition, the positive quadrivalent lanthanide ion orbital hybridization charge transition is allowed by selection law and is 10 more than f-f transition in strength6Above, and with broad spectral absorption, the absorption spectrum is much wider than the f-f transition, and even wider than the f-d transition, so the orbital hybrid charge transition of lanthanide ions can absorb very strong broad spectrum light.
In the lanthanoid elements, Ce, Pr and Tb can have positive quadrivalent ions, wherein Ce4+Most stable, Tb4+And Pr4+Unstable in the solid state. Nd and Dy also have positive quadrivalent ions in special cases, but are extremely unstable. Compared with Pr4+And Tb4 +，Ce4+Higher energy required for orbital hybrid charge transition, so Ce4+The orbital hybrid transition of (A) generally only absorbs ultraviolet light and hardly absorbs blue light, so that Ce is doped in an oxide semiconductor4+The improvement of the photostability is limited. And Pr4+And Tb4+Energy required for transition of (2) is compared with Ce4+The low-emission red-green light can absorb blue light and even red-green light, and further down-convert the blue light into low-energy light or a non-radiation form, thereby avoiding the threshold voltage drift phenomenon caused by the ionization and the release of electrons by the absorption of the blue light by oxygen vacancies in the oxide semiconductor. As shown in FIG. 4, Ce4+Has an absorption edge of about 4.0eV and is also located in the UV region. Tb4+And Pr4+Is located in the blue region. And Nd4+And Dy4+Although it also absorbs visible light, it is very unstable.
In the solid containing the n-tetravalent lanthanide ion, the n-trivalent lanthanide ion is generally present at the same time, and the above analysis shows that the n-trivalent lanthanide ion has little effect on the improvement of NBIS stability, and also affects electron transport and lowers mobility. Furthermore, the positive trivalent lanthanide ion radius is much larger than the positive tetravalent lanthanide ion, much larger than In the host oxide semiconductor material3+、Zn2+、Ga3+And Sn4+Radius (all are less than
) Therefore, the lattice relaxation of the host oxide semiconductor material doped with trivalent positive lanthanide ions is much more severe and the mobility is lower than the lattice relaxation of the host oxide semiconductor material doped with tetravalent positive lanthanide ions. Therefore, in the case where the amount of the lanthanide ion (including positive tetravalent and other valence states) to be incorporated is constant, the greater the ratio of the amount of the positive tetravalent lanthanide ion to the amount of the lanthanide ion in the other valence state, the more significant the effect of improving the light stability. Similarly, for a given number of tetravalent lanthanide ions incorporated, the greater the ratio of the number of positive tetravalent lanthanide ions to the number of lanthanide ions in other valence states, the less the total number of lanthanide ions (including positive tetravalent and other valence states) contained in the material, the less scattering the electrons, and the higher the mobility.
In addition, due to concentration quenching, the positive trivalent lanthanide ion can affect the absorption of light by the positive tetravalent lanthanide ion. Thus, the ratio of the number of positive tetravalent lanthanide ions to the number of lanthanide ions in other valencies is greater than 0.1. More preferably, the ratio of the number of positive tetravalent lanthanide ions to the number of lanthanide ions in other valences is greater than 1. More preferably, the ratio of the number of positive tetravalent lanthanide ions to the number of lanthanide ions in other valences is greater than 2. Most preferably, all lanthanide ions are positive tetravalent.
The doping amount of the lanthanide ions required by the oxide semiconductor target material is less because the ratio of the number of the positive tetravalent lanthanide ions to the number of the lanthanide ions in other valence states is higher. Preferably, the ratio of the number of lanthanide ions to the number of all cations is between 0.05% and 10%. More preferably, the ratio of the number of lanthanide ions to the number of all cations is between 0.05% and 5%.
The invention breaks through the limit that the target material made of the conventional lanthanide element is trivalent, and develops a new technical scheme that the oxide semiconductor target material contains positive quadrivalent terbium ion. An oxide semiconductor target having a positive tetravalent lanthanide ion is formed using a host oxide semiconductor material for use in the preparation of a channel layer as a thin film transistor. Due to the characteristic of lower energy required by the orbital hybridization transition of the positive quadrivalent lanthanide ions, when the thin film transistor is illuminated, blue light and even red light can be absorbed and further converted into a non-radiative or low-energy light form, so that the problems of increased conductance and negative drift of threshold voltage caused by ionization of oxygen vacancies by the blue light in a backlight source or self-luminescence are avoided, and the illumination stability of the device is improved; under illumination and negative gate voltage stress (NBIS), the problem of negative drift of the threshold voltage of the device can be solved, and the TFT has good stability under illumination, particularly under NBIS; the problem of complicated preparation process is avoided, impurities or crystal field splitting energy level defects are not introduced, electron transport is not influenced, and the TFT device with good NBIS stability and high mobility is realized.
Example 2.
An oxide semiconductor target material, which comprises a matrix oxide semiconductor material and positive quadrivalent terbium ion Tb4+。
Incorporating only Tb in the host oxide semiconductor material4+The oxide semiconductor target material and the prepared thin film transistor have high electron mobility and NBIS performance stability. Experiments show that Tb is doped compared with other elements4+The performance of (2) is optimal.
Tb4+Contains 7 f electrons and is in a relatively stable half-full state, so Tb4+Can effectively avoid the influence of crystal field, namely different host oxide semiconductor material environments and oxygen vacancy environments on Tb4+The influence of the electronic structure is small. Thus, Tb is doped in the host oxide semiconductor material4+Can improve the mobility and stability and widen the process window.
In addition, in the case of the present invention,
has an ionic radius close to that in the host oxide semiconductor material
And
of (c) is used. Thus, Tb is doped in the host oxide semiconductor material4+The crystal lattice relaxation is small, the damage to the crystal lattice is small, and the mobility is high. Tb4+Absorbing blue light and converting the blue light into a non-radiation form without the influence of other stray light, so Tb4+The doping is more effective for improving the photostability of the oxide semiconductor. Thus, the positive tetravalent lanthanide ion is Tb4+The oxide semiconductor target material has the best performance.
Example 3.
An oxide semiconductor thin film is prepared by a physical vapor deposition method, the thickness is 3-200nm, and the target material used in the physical vapor deposition is the oxide semiconductor target material comprising the matrix oxide semiconductor material and the positive tetravalent lanthanide ion in the embodiment 1 or 2. Such physical vapor deposition includes, but is not limited to, sputtering (including dc sputtering, rf sputtering, or reactive sputtering), pulsed laser deposition, atomic layer deposition, and the like.
It is noted that the oxide semiconductor thin film may be prepared by two or more targets, at least one of which contains Tb4+And then the target materials are arranged on different target positions to obtain the oxide semiconductor film by a double-target or multi-target codeposition method.
The oxide semiconductor film prepared by the invention can absorb blue light and is used as a channel layer of a thin film transistor, so that the semiconductor thin film transistor has good device stability under illumination, particularly under NBIS, the good mobility and subthreshold performance of the thin film transistor are kept, the problem of complicated preparation process is avoided, impurities are not introduced, and the performance of the device can be ensured.
Example 4.
A transistor, which is of a bottom-gate top-contact type in structure, as shown in fig. 1, is provided with: the semiconductor device includes a substrate 10, a gate electrode 11 positioned on the substrate 10, an insulating layer 12 positioned on the substrate 10 and the gate electrode 11, a channel layer 13 covering an upper surface of the insulating layer 12 and corresponding to the gate electrode 11, and a source electrode 14a and a drain electrode 14b spaced apart from each other and electrically connected to both ends of the channel layer 13. Among them, the channel layer 13 is the oxide semiconductor thin film including the host oxide semiconductor material and the positive tetravalent lanthanoid ion in embodiment 2.
The substrate 10 may be one of substrate materials such as glass, flexible polymer substrate, silicon wafer, metal foil, quartz, etc., and may further include a buffer layer or a water-oxygen barrier layer, etc., which covers the substrate.
The material of the gate 11 may be a conductive material, such as a metal, an alloy, a conductive metal oxide, doped silicon, a conductive polymer, or a stack of two or more thin films made of any combination of the above materials.
The insulating layer 12 may be a single-layer film made of an insulating material used for a semiconductor device, such as silicon oxide, silicon nitride, silicon oxynitride, aluminum oxide alloy, ytterbium oxide, titanium oxide, hafnium oxide, tantalum oxide, zirconium oxide, a polymer insulating material, a photoresist, or a stack of two or more layers made of any combination of the above materials.
The material of the source electrode 14a and the drain electrode 14b may be a single-layer film of a conductive material, such as a metal, an alloy, a conductive metal oxide, a conductive polymer, or a stack of two or more layers of films made of any combination of the above materials.
The transistor of the present invention may be a closed structure including only a substrate, a gate electrode, an insulating layer, a channel layer, a source electrode, and a drain electrode, may further include an etch stopper layer, a passivation layer, a pixel defining layer, or the like, and may be integrated with other devices, or the like.
The transistor can be prepared by the following method:
(1) one or more layers of conductive films with the thickness of 100-500 nm are prepared by a sputtering method, and the conductive films are patterned by a shielding mask or photoetching method to obtain the grid electrode.
(2) And then preparing the insulating layer by spin coating, drop coating, printing, anodic oxidation, thermal oxidation, physical vapor deposition or chemical vapor deposition, wherein the thickness is 100-1000 nm, and patterning the insulating layer by a shielding mask or photoetching method to obtain the insulating layer.
(3) The channel layer is prepared by a pulse laser deposition method, and is patterned by a mask UV irradiation method.
(4) Preparing one or more layers of conductive films by a vacuum evaporation or sputtering method, wherein the thickness of the conductive films is 100-1000 nm, and patterning by a mask or photoetching method to obtain a source electrode and a drain electrode simultaneously.
The transistor adopts the film containing the positive tetravalent terbium ions as the channel layer, and because the energy required by the orbital hybridization transition of the positive tetravalent terbium ions is lower, when the thin film transistor is illuminated, the thin film transistor can absorb blue light and even red and green light and further down convert the blue light and the red and green light into a non-radiation form, thereby avoiding the problems of increased conductance and negative drift of threshold voltage caused by ionization of oxygen vacancy by the blue light in a backlight source or self-luminescence, and improving the illumination stability of a device; under illumination and negative gate voltage stress (NBIS), the problem of negative drift of the threshold voltage of the device can be solved, and the TFT has good stability under illumination, particularly under NBIS; the problem of complicated preparation process is avoided, impurities or crystal field splitting energy level defects are not introduced, electron transport is not influenced, and the TFT device with good NBIS stability and high mobility is realized.
Therefore, the oxide semiconductor target, the thin film and the transistor can keep high mobility and improve NBIS stability.
Example 5.
An oxide semiconductor target comprising a matrix oxide semiconductor material and a positive tetravalent lanthanide ion. Wherein the matrix oxide semiconductor material is indium oxide (In)2O3) And the positive tetravalent lanthanide ion is Tb4+. Positive tetravalent lanthanide ions Tb4 +The ratio of the amount to the amount of all cations was 3%.
The target material is prepared by the following method: the terbium oxide powder is further oxidized, is uniformly mixed with the matrix oxide semiconductor material powder after being ground, is sintered in an ozone atmosphere, is formed by cold isostatic pressing after being ground and mixed for the second time, and is sintered at the temperature of 1400 ℃ in a pure oxygen atmosphere. The total content of Tb with different valence states in the target material is 3%, and the Tb content of the target material with 3% of Tb content is regulated by regulating the above-mentioned oxidation condition and sintering atmosphere4+/Tb3+Are controlled to 1/1 and 1/0, respectively, i.e., their Tb4+The contents of (A) are 1.5% and 3%, respectively.
FIG. 5 shows different Tb4+The reflection spectrum of the doped target shows that the target is not doped with Tb (pure In)2O3) Strong reflection at a wavelength of about 400-1000nm, indicating that the absorption in this wavelength region is very weak (since the target is opaque, the reflectance + absorptance can be approximated as 1); and In2O3Incorporation of 3% Tb (Tb)4+/Tb3+1/0) has very weak reflection in the 400-1000nm region, indicating that the absorption in this wavelength region is very strong; in2O3Incorporation of 3% Tb (Tb)4+/Tb3+1/1) target material is doped with 3% Tb (Tb) in the reflection ratio of 400-1000nm interval4+/Tb3+1/0) was increased, indicating Tb in the target material4+Absorption in the visible region is predominantAnd (4) acting.
Example 6.
A transistor, as shown in fig. 1, is prepared as follows: first, an Al — Nd alloy thin film having a thickness of 300nm is formed on a glass substrate by sputtering, and patterned by photolithography to obtain the gate electrode 11. The insulating layer 12 is then formed by anodization to form an alumina gate oxide layer. The channel layer 13 was prepared by sputtering, using the same target as that used in example 5, and the thickness of the channel layer 13 was 10 nm. An Indium Tin Oxide (ITO) thin film with a thickness of 500nm is formed on the channel layer 13 by sputtering, and patterned by using a shadow mask, thereby obtaining a source electrode 14a and a drain electrode 14 b.
FIG. 6 shows the utilization of In2O3Incorporation of Tb4+/Tb3+Tb 4p peak spectrum of X-ray photoelectron Spectroscopy (XPS) of a film prepared by sputtering a target with a ratio of 1/1 was calculated4+And Tb3+The content ratio of (A) was 53.3%/46.7% (as shown in Table 1), which deviated from the composition of the target material, but was substantially the same. In is to be noted2O3The film is transparent in visible light, so that the absorption of the film with a small thickness (within 1000 nm) and a small Tb doping amount (within 10%) in the visible light region is much weaker than that of a corresponding target material, even weaker than the absorption fluctuation amount caused by the microcavity effect, which is a normal phenomenon.
Based on different Tb4+The transfer characteristics of the Thin Film Transistor (TFT) under NBIS (white light illumination of the LED plus a gate bias of-20V) are shown in FIGS. 7, 8 and 9. Wherein, FIG. 7 shows pure In2O3Transfer characteristic curve under NBIS of the thin film transistor without doping Tb; FIG. 8 shows In2O3Incorporating 3% Tb, and Tb4+/Tb3+1/0 (i.e. only doped with Tb)4+) Transfer characteristic curve under NBIS of the thin film transistor in the case; FIG. 9 is In2O3Incorporation of 3% Tb, and Tb4+/Tb3+Transfer characteristics under NBIS of the thin film transistor in the case of 1/1. For comparison, conventional targets were also usedPreparation method prepares only Tb3+(i.e. not containing Tb)4+) Doped In2O3Target material (i.e. 3% Tb (Tb))4+/Tb3+0/1)) based on different Tb4+The transfer properties of the Thin Film Transistors (TFTs) at NBIS (white light illumination of the LED plus a gate bias of-20V) are listed in Table one.
It can be seen that pure In2O3The mobility of TFT can reach 39.5cm2Vs, but the amount of drift of the threshold voltage (Δ V) under NBISth) But reaches-14.0V, the NBIS stability of the device is poor. When 3% Tb (Tb) is doped4+/Tb3+1/0), the mobility was 38.1cm2/Vs, whose NBIS lower threshold voltage hardly drifts (Δ V)thonly-0.01V). When 3% Tb (Tb) is doped4+/Tb3+1/1), the mobility dropped to 33.2cm2/Vs, Δ V under NBISthis-0.06V. When 3% Tb (Tb) is doped4+/Tb3+0/1), the mobility dropped to 19.5cm2V, [ delta ] V under NBIS of, [ delta ] VsthIt was-13.1V. This indicates that In is simple2O3The negative shift of the threshold voltage under NBIS of a TFT is severe. By adding Tb only3+The ions have little improvement effect on the negative drift of the threshold voltage of the NBIS device, and the mobility is greatly reduced, which cannot meet the requirements because of Tb3+The visible light cannot be absorbed, and the blue light cannot be down-converted; and Tb3+The crystal contains 8 f electrons, is more than half full, is easy to be split under the action of a crystal field to form a large number of defect energy levels, and causes the reduction of mobility. Therefore, only Tb3+The problem of negative drift of NBIS cannot be solved, and the mobility is low. Containing Tb4+The phenomenon of NBIS lower threshold voltage shift of the device is obviously improved, and especially only Tb is contained4+(not containing Tb)3+) The NBIS lower threshold voltage of the device has little drift. Reduction of Tb4+/Tb3+The ratio of (a) will decrease mobility and NBIS stability.
Watch 1
It can be seen that Tb is adopted4+Doped In2O3The transistor as the channel layer can effectively improve the NBIS stability while maintaining high mobility.
Example 7.
An oxide semiconductor target comprising a matrix oxide semiconductor material and a positive tetravalent lanthanide ion. Wherein the matrix oxide semiconductor material is InSnZnO, and the positive quadrivalent lanthanide ion is Tb4+. The target material is prepared by the following method: the terbium oxide powder is further oxidized, is uniformly mixed with the matrix oxide semiconductor material powder after being ground, is sintered in a strong oxidizing atmosphere, is formed by cold isostatic pressing after being ground and mixed for the second time, and is sintered in the strong oxidizing atmosphere. The total content of Tb in different valence states in the target material is 5%, and all Tb can be controlled to be Tb by regulating the above-mentioned oxidation condition and sintering atmosphere4+。
A transistor, as shown in fig. 10, is provided with: the semiconductor device includes a substrate 10, a gate electrode 11 on the substrate 10, a gate insulating layer 12 on the substrate 10 and the gate electrode 11, a channel layer 13 covering an upper surface of the gate insulating layer 12 and above the gate electrode 11, an etch stop layer 17 covering the channel layer, and a source electrode 14 and a drain electrode 15 spaced apart from each other and electrically connected to both ends of the channel layer 13 and the etch stop layer 14.
The substrate 10 is glass (containing a water oxygen barrier layer), the Mo/Al/Mo electrode is prepared on the substrate 10 by sputtering, the total thickness is 400nm, and the gate electrode 11 is formed by coating photoresist, exposing, developing, and the like.
Preparation of SiN on the substrate 10 on which the gate electrode 11 is formed by Plasma Enhanced Chemical Vapor Deposition (PECVD)x/SiO2The stacked films were used as the gate insulating layer 12, and the total thickness was 320 nm.
The channel layer 13 is made of tbinssnzno and is prepared by a sputtering method, and the thickness of the channel layer is 40 nm. The specific manufacturing process of the channel layer 13 is as follows: the target material described in the present example was mounted on a target site, film-formed by sputtering, and patterned by photolithography.
Preparing a layer of SiO with a thickness of 100nm on the substrate 10 on which the channel layer 13 is formed by using a PECVD method2The thin film is patterned by dry etching to form an etching stopper layer 17.
The Mo/Al/Mo electrode is formed on the substrate 10 on which the etching stopper layer 17 is formed by using a sputtering method, the total thickness is 600nm, and the source electrode 14 and the drain electrode 15 are formed by using steps of coating a photoresist, exposing, developing, and the like.
After the device is prepared, annealing is carried out for 1h at 350 ℃ in the atmosphere.
For the thin film transistors prepared by the process and with different raw material ratios and the comparative examples, the corresponding delta V is tested by adopting LED white light irradiation and grid bias voltage of-25Vth(V) and mobility, the results are shown in Table II.
TABLE II TbInSnZnO TFT device Performance (Tb) at different In/Sn/Zn ratios4+The content is 5%)
It can be seen that the use of the additive containing Tb4+The transistor with the doped oxide semiconductor material as the channel layer can effectively improve the NBIS stability and simultaneously keep higher mobility.
The oxide semiconductor film can be used as a channel layer material of a transistor. The oxide semiconductor film and the thin film transistor thereof are mainly used for active drive of organic light emitting display, liquid crystal display or electronic paper, and can also be used for integrated circuits.
Example 8.
An oxide semiconductor target material, which comprises a matrix oxide semiconductor material and positive quadrivalent terbium ion Tb4+. Wherein the matrix oxideThe semiconductor material is a mixture of three oxides of In, Sn and Zn, wherein In: sn: zn 77/10/10. The target material is prepared by the following method: the terbium oxide powder is further oxidized, is uniformly mixed with the matrix oxide semiconductor material powder after being ground, is sintered in a strong oxidizing atmosphere, is formed through cold isostatic pressing after being ground and mixed for the second time, and is sintered in the strong oxidizing atmosphere. The total content of Tb in different valence states in the target material is 5%, and Tb is controlled by regulating the above-mentioned oxidation condition and sintering atmosphere4+/Tb3+The ratio of (a) to (b). A thin film transistor was manufactured by the same process as in example 7. Adopting LED white light irradiation plus-25V grid bias voltage test to test corresponding delta V for the prepared thin film transistorth(V) and mobility, the results are shown in Table III.
Table III different Tb4+/Tb3+Proportional TFT device Performance
| Tb4+/Tb3+ | Mobility (cm2/Vs) | Δ Vth (V) under NBIS |
| Tb4+/Tb3+＝1/0 | 52.1 | -0.8 |
| Tb4+/Tb3+＝10/1 | 48.5 | -0.85 |
| Tb4+/Tb3+＝5/1 | 46.2 | -0.9 |
| Tb4+/Tb3+＝2/1 | 40.3 | -1.05 |
| Tb4+/Tb3+＝1/2 | 36.7 | -2.32 |
| Tb4+/Tb3+＝1/10 | 24.9 | -3.47 |
| Tb4+/Tb3+＝1/20 | 18.9 | -7.50 |
As can be seen, Tb4+The introduction of (2) plays a major role in the NBIS stability of the device and can maintain good mobility of the device. Tb4+/Tb3+The higher the ratio of (a), the better the mobility and NBIS stability of the device.
Example 9.
An oxide semiconductor target comprising a matrix oxide semiconductor material and a positive tetravalent lanthanide ion. Wherein the matrix oxide semiconductor material is indium oxide (In)2O3) The positive tetravalent lanthanide ion is positive tetravalent cerium (Ce)4+). The target material is prepared by the following method: firstly, grinding Ce oxide, uniformly mixing with matrix oxide semiconductor material powder, sintering in a strong oxidizing atmosphere, grinding and mixing for the second time, forming by cold isostatic pressing, and sintering in the strong oxidizing atmosphere. The Ce content was 3%. Adjusting the oxidation condition and sintering atmosphere to obtain the Ce of the target material4+/Ce3+The ratio of (A) to (B) was controlled to be 1/0 (i.e., containing no Ce)3+). For comparison, dysprosium (Dy) and ytterbium (Yb) -doped indium oxide were prepared under the same target preparation conditions, Dy (Dy) was not likely to form positive quadrivalence under any conditions, and both the valence states were measured to be positive trivalent, so Dy was4+/Dy3+And Dy4+/Dy3+Both 0/1.
A thin film transistor was fabricated by the same process as in example 6, and the fabricated thin film transistor was subjected to a gate bias test of-20V plus white light from LEDth(V) and mobility, the results are shown in Table four. It can be seen that the NBIS stability of all three doped TFTs is poor.
Watch four
| Ce. Dy and Yb content | Mobility (cm)2/Vs) | Δ V under NBISth(V) |
| 0% (pure In)2O3) | 39.5 | -14.0 |
| 3％(Ce4+/Ce3+＝1/0) | 30.5 | -12.8 |
| 3％(Dy4+/Dy3+＝0/1) | 17.2 | -13.4 |
| 3％(Yb4+/Yb3+＝0/1) | 16.9 | -13.3 |
Example 10.
An oxide semiconductor target comprising a matrix oxide semiconductor material and a positive tetravalent lanthanide ion. Wherein the matrix oxide semiconductor material is indium oxide (In)2O3) The positive tetravalent lanthanide ion is Pr4+. The target material is prepared by the following method: firstly, blending and oxidizing praseodymium oxide powder, uniformly mixing the praseodymium oxide powder with matrix oxide semiconductor material powder after grinding, then sintering the mixture in a strong oxidizing atmosphere, carrying out secondary grinding and mixing, then carrying out cold isostatic pressing and sintering the mixture in the strong oxidizing atmosphere. Two targets with different Pr doping amounts are prepared, and the Pr content is 3 percent and 7 percent respectively. Adjusting the oxidation condition and sintering atmosphere to obtain two kinds of Pr with different Pr contents4+/Pr3+The ratios of (A) were controlled to 1/1.
FIG. 11 shows the reflection spectra of the target materials with different Pr doping amounts, and it can be seen that the target material without Pr doping (pure In)2O3) Strong reflection at a wavelength of about 400-1000nm, indicating that the absorption in this wavelength region is very weak (since the target is opaque, the reflectance + absorptance can be approximated as 1); and In2O3Doped with 3% Pr (Pr)4+/Pr3+1/1) is relatively weak at the 400-1000nm interval, indicating that the absorption is strong in this wavelength interval; in2O3Doped with 7% Pr (Pr)4+/Pr3+1/1) has increased reflection in the 400-. This is mainly due to Pr4+Or Pr3+Is caused by the f electron in (1). While the incorporation of Tb does not have this problem.
Therefore, the target preparation method can form the positive quadrivalent praseodymium on the target.
Example 11.
A transistor, as shown In FIG. 1, is prepared In the same manner as In example 6, except that the target material for the channel layer 13 of the thin film transistor is Pr-doped In example 102O3A target material.
FIGS. 12 and 13 show the difference based on Pr4+The transfer characteristics of the Thin Film Transistors (TFTs) under NBIS (white light illumination of the LED plus a gate bias of-20V) are reported in Table five. It can be seen that the mobility was 18.9cm when 3% of Pr was doped2Vs, NBIS lower threshold voltage shift amount (Δ V)th) is-4.1V, and has NBIS stability higher than that of pure In2O3TFT is improved; however, Tb was added in the same concentration as the mixed solution4+In2O3By comparison of TFT with Pr doping4+In2O3The mobility and NBIS stability of TFT are poor, and there is obvious hump effect in subthreshold region, i.e. current is turned on in advance, off-state current (I)off) Enlargement, mainly associated with oxygen vacancies or Pr4+The crystal contains one f electron, and is easily influenced by a crystal field to form a large number of defect energy levels, so that electron transportation is influenced, and mobility is reduced.
When 7% of Pr was doped, the mobility rapidly decreased to 9.2cm2Vs, NBIS lower threshold voltage shift amount (Δ V)th) The positive drift is +0.5V in the first 100s, and the negative drift is-1.2V in the last 3500 s; when the gate voltage (V)GS) When the voltage is more than 5V, NBIS lower threshold voltage drift rule and VGSThe opposite is true below 5V. This suggests that two mechanisms work simultaneously when high concentration Pr is doped: firstly, the light absorption caused by concentration quenching is reduced, and the down-conversion effect is weakened; secondly, due to Pr4+The f electrons exist, and are split under the influence of a crystal field to cause a large number of electron traps, which are used as recombination mediators of ionized oxygen vacancy electrons to reduce the service life of photo-generated electrons, and are also used as traps of common carriers to capture the carriers at higher concentration, so that the threshold voltage is just floated at the beginning. In contrast, Tb is doped4+In (2) of2O3The TFT does not have this phenomenon. In addition, Pr down-converts green light after absorbing blue light, and the oxygen vacancy level is raised due to the interface band at negative gate voltage as shown in fig. 14Up-shifting so green light also has a partial effect on NBIS.
Watch five
Thus, using Pr4+Doped In2O3The transistor as the channel layer has limited improvement in NBIS stability of the device, and the mobility of the device is greatly reduced. Thus, Pr doping does not meet the object of the present invention.
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention and not for limiting the protection scope of the present invention, and although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.
Claims (10)
1. An oxide semiconductor target, characterized in that: the material comprises a host oxide semiconductor material and positive quadrivalent lanthanide ions, wherein the host oxide semiconductor material contains at least one of five elements of In, Zn, Sn, Ga and Cd.
2. The oxide semiconductor target according to claim 1, wherein: the positive tetravalent lanthanide ion is positive tetravalent terbium ion Tb4+。
3. The oxide semiconductor target according to claim 2, wherein: tb4+Ion number and Tb3+The ratio of the number of ions is greater than 0.1.
4. The oxide semiconductor target according to claim 3, wherein: tb4+Ion number and Tb3+The ratio of the number of ions is greater than 1.
5. Oxygen according to claim 4A compound semiconductor target material is characterized in that: containing only Tb4+Does not contain Tb3+。
6. The oxide semiconductor target according to any one of claims 1 to 5, wherein: the preparation method comprises the following steps of uniformly mixing oxide powder of elements corresponding to positive tetravalent lanthanide ions and matrix oxide semiconductor material powder, sintering in a strong oxidizing atmosphere, grinding and mixing for the second time, forming by cold isostatic pressing or hot pressing, and sintering in the strong oxidizing atmosphere to obtain the oxide semiconductor target.
7. An oxide semiconductor thin film, which is prepared by a physical vapor deposition method with a thickness of 3 to 200nm, wherein the oxide semiconductor target used for the physical vapor deposition is the oxide semiconductor target as defined in any one of claims 1 to 6.
8. A method for improving stability and mobility of a thin film transistor,
preparing an oxide semiconductor target material, wherein the oxide semiconductor target material comprises a matrix oxide semiconductor material and positive tetravalent lanthanide ions serving as functional ions, the functional ions can perform orbital hybridization, the energy required by orbital hybridization transition is not higher than that of blue light, and the functional ions are converted into a non-radiative form after orbital hybridization transition;
depositing an oxide semiconductor thin film for use as a channel layer of a thin film transistor through the oxide semiconductor target;
when the thin film transistor has illumination or illumination and negative grid bias voltage, the functional ions absorb blue light and even red and green light to realize orbital hybrid transition and convert the blue light and the red and green light into a non-radiative form; and the ionization of oxygen vacancies is prevented by absorbing illumination through the hybridization transition of functional ion orbitals, so that the serious lattice relaxation and the threshold voltage drift are avoided.
9. The method of improving stability and mobility of a thin film transistor according to claim 8,characterized in that the positive quadrivalent lanthanide ion is Tb4+，Tb4+Ion number and Tb3+The ratio of the number of ions is greater than 0.1.
10. A thin film transistor characterized in that a channel layer contains one or more oxide semiconductor layers, at least one of which is an oxide semiconductor thin film prepared by the method of any one of claims 7 to 9;
the thin film transistor is used as a driving back plate of display or used for an internal memory, a flash memory and a dynamic random access memory.
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| US20100108502A1 (en) * | 2006-12-13 | 2010-05-06 | Idemitsu Kosan Co., Ltd. | Sputtering Target and Oxide Semiconductor Film |
| US20110315936A1 (en) * | 2007-03-20 | 2011-12-29 | Idemitsu Kosan Co., Ltd. | Sputtering target, oxide semiconductor film and semiconductor device |
| US20210083126A1 (en) * | 2017-11-15 | 2021-03-18 | South China University Of Technology | Metal oxide (mo) semiconductor and thin-film transistor and application thereof |
| CN112582466A (en) * | 2020-11-20 | 2021-03-30 | 华南理工大学 | Metal oxide semiconductor, thin film transistor and application |
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| US20100108502A1 (en) * | 2006-12-13 | 2010-05-06 | Idemitsu Kosan Co., Ltd. | Sputtering Target and Oxide Semiconductor Film |
| US20110315936A1 (en) * | 2007-03-20 | 2011-12-29 | Idemitsu Kosan Co., Ltd. | Sputtering target, oxide semiconductor film and semiconductor device |
| US20210083126A1 (en) * | 2017-11-15 | 2021-03-18 | South China University Of Technology | Metal oxide (mo) semiconductor and thin-film transistor and application thereof |
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| CN116813310B (en) * | 2023-06-01 | 2024-06-07 | 先导薄膜材料（广东）有限公司 | Rare earth element doped indium tin gallium oxide target material and preparation method thereof |
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