The field of the currently claimed embodiments of this invention relates to electronic devices and methods of producing the electronic devices, and more particularly to electronic devices and methods of producing the electronic devices to have an oxide thin film with content gradient.
An aspect of the present invention is to provide an electronic device. The electronic device includes a first electrode; and a second electrode spaced apart from the first electrode. The device further includes a conduction channel in electrical connection with the first and second electrodes so as to be able to conduct a charge carrier current between the first and second electrodes along a condition path during an operating condition. The conduction channel has a gradient semiconductor oxide composition transverse to the conduction path such that the gradient semiconductor oxide composition varies from indium rich to gallium rich.
Another aspect of the present invention is to provide a method of producing a conduction channel for an electronic device. The method includes forming a first indium-rich metal-oxide gel film at least one of on or above a substrate; forming a second indium rich metal-oxide gel film at least one of on or above the first indium-rich metal-oxide gel film, the second indium rich metal-oxide gel film being less indium rich than the first indium-rich metal-oxide gel film; forming a gallium-rich metal-oxide gel film at least one of on or above the second indium-rich metal-oxide gel film; and annealing the conduction channel to remove solvent molecules and volatile impurity elements and to form a cross-linked metal-oxygen framework.
Yet another aspect of the present invention is to provide an electronic device produced according to the above method.
The present disclosure, as well as the methods of operation and functions of the related elements of structure and the combination of parts and economies of manufacture, will become more apparent upon consideration of the following description and the appended claims with reference to the accompanying drawings, all of which form a part of this specification, wherein like reference numerals designate corresponding parts in the various figures. It is to be expressly understood, however, that the drawings are for the purpose of illustration and description only and are not intended as a definition of the limits of the invention.
Some embodiments of the current invention are discussed in detail below. In describing embodiments, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. A person skilled in the relevant art will recognize that other equivalent components can be employed and other methods developed without departing from the broad concepts of the current invention. All references cited anywhere in this specification, including the Background and Detailed Description sections, are incorporated by reference as if each had been individually incorporated.
Some embodiments of the current invention are directed to methods to prepare metal-oxide semiconductor thin-films with cation concentration gradient by sol-gel processes and their application as channel materials to realize thin film transistors (TFTs) with high field-effect mobility and good stability as compared to thin-films with uniform cation distribution. According to an embodiment, heterogeneous gel-films are first formed by alternatively spin-coating precursor solutions with different compositions. Ion diffusion occurs during an ensuing thermal annealing process that leads to the desired cation ion concentration gradient. The following describes the example of metal oxide semiconductors consisting of post-transition metal ions such as indium, gallium, zinc and tin, prepared by a method according to an embodiment of the current invention. Indium-rich films (such as In2O3, 9:1:2 InGaZnO, InZnO, etc.) are used as the bottom layer to provide high carrier density and fast electronic conduction pathways, while gallium-rich films (such as Ga2O3, GaZnO, etc.) are used on the top to suppress the off-state current and improve the stability under harsh environments. Detailed description of the data can be found below.
1. Precursor solution preparation: Metal salts, such as In(NO3)3, Ga(NO3)3, Zn(CH3COO)2, are dissolved in appropriate solvents such as 2-methoxyethanol or water, with a total metal ion concentration of 0.1 M. Acetylacetone is added as a solution stabilizer. The solution is stirred and ages for 3-6 hours before use. The general concepts of the current invention are not limited to only these particular precursor solutions, nor to the particular aging time.
2. Metal-oxide thin-film formation: The precursor solution prepared in step 1 is spin-coated on a Si wafer, glass or plastic substrates with a spinning speed of about 2000-4000 rpm and time of 10-30 seconds. The substrates are cleaned and treated by UV ozone for at least 20 minutes before spin coating the precursor solution. After spin coating, soft-baking at 100-200° C. for 1-5 min renders a gel film. Multiple runs of spin coating and soft-baking are carried out to achieve desired film thickness or multiple film stacking. Finally, the gel film is annealed at elevated temperatures (200-400° C.) for 1-3 hours to remove solvent molecules and volatile impurity elements, and to form cross-linked metal-oxygen framework. These steps and parameters are examples and do not limit the general concepts of this invention.
3. Metal-oxide compositional engineering: An embodiment of this invention is directed to use a multiple-layer stacking strategy to realize desired composition engineering. One or more layers of In-rich gel films are first formed on the substrate by successive spin-coating and soft-baking as described in step 2. Then, one or more less-In-rich gel-films are formed by the same method. The general concepts of the current invention are not limited to the particular number of In-rich gel films, nor to the specific difference in composition between layers in the stack. Both the number of layers and the differences in composition between layers can be selected according to the particular application. Subsequently, gallium-rich films are coated and, if needed, more-gallium-rich films can be used to finalize the film formation. The general concepts of the current invention are not limited to the particular number of gallium-rich thin films used, nor to the particular difference in composition between the gallium-rich thin films. Both can be chosen according to the particular application. The multiple-layered films are finally annealed using the method described in step 2. This process eventually produces a metal-oxide thin-film with an indium-content (gallium-content) gradient, as shown in
Therefore, the method of producing a conduction channel for an electronic device includes 1) forming a first indium-rich metal-oxide gel film at least one of on or above a substrate; 2) forming a second indium rich metal-oxide gel film at least one of on or above the first indium-rich metal-oxide gel film, the second indium rich metal-oxide gel film being less indium rich than the first indium-rich metal-oxide gel film; 3) forming a gallium-rich metal-oxide gel film at least one of on or above the second indium-rich metal-oxide gel film; and 4) annealing the conduction channel to remove solvent molecules and volatile impurity elements and to form a cross-linked metal-oxygen framework.
In an embodiment, the method further includes, before the annealing, forming a third indium rich metal-oxide gel film at least one of on or above the first indium-rich metal-oxide gel film and prior to forming the second indium rich metal-oxide gel film, the third indium rich metal-oxide gel film being less indium rich than the first indium-rich metal-oxide gel film and more indium rich than the second indium-rich metal-oxide gel film.
In an embodiment, the method further includes, before the annealing, forming a second gallium-rich metal-oxide gel film at least one of on or above the first gallium-rich metal-oxide gel film, the second gallium-rich metal-oxide gel film being more gallium rich than the first gallium-rich metal-oxide gel film.
In an embodiment, forming the first indium-rich metal-oxide gel film includes spin coating a first precursor solution followed by a first soft baking. In an embodiment, forming the second indium-rich metal-oxide gel film includes spin coating a second precursor solution followed by a second soft baking. In an embodiment, forming the gallium-rich metal-oxide gel film includes spin coating a third precursor solution followed by a third soft baking.
The device 100 also includes a conduction channel 106. The conduction channel 106 is in electrical connection with the first electrode 102 and second electrode 104 so as to be able to conduct a charge carrier current between the first electrode 102 and the second electrode 104 along a conduction path during an operating condition. The conduction channel 106 includes a gradient semiconductor oxide composition transverse to the conduction path such that the gradient semiconductor oxide composition varies from indium rich to gallium rich, as shown in
In an embodiment, the device 100 also includes passivation layer 112 so as to further improve the stability of the device 100. In an embodiment, the passivation layer 112 includes PECVD SiO2. In an embodiment, as shown in
In an embodiment, the electronic device 100 shown in
4. TFT fabrication: In an embodiment, the metal-oxide thin-film transistor device 100 adopts a bottom-gate, staggered configuration. Heavily doped silicon or pre-formed metal patterns are used as global or local gate, while thermal SiO2, ALD-deposited Al2O3 or PECVD SiO2 are used as gate insulator. After forming the desired metal-oxide thin-films as channel semiconductors, S/D electrodes are deposited and patterned either through a shadow mask or by lithography. Finally, the devices are encapsulated with PECVD SiO2 to ensure a good stability under long-term operation.
Multi-cation metal-oxides with different compositions, i.e. different ratios of various metal ions, exhibit distinct electronic properties. Indium-rich oxides feature high carrier concentration because of the low dissociation energy of In—O bonds and thus high concentration of oxygen-vacancies, the primary contributor of free carriers, and high carrier mobility due to the large overlaps between neighboring spherical 5s-orbitals of indium that provide more electronic conduction pathways. Consequently, indium-rich films result in TFTs with high output-current. However, the tendency of forming oxygen-vacancies leads to poor stability of In-rich films and makes it difficult to achieve TFTs with enhancement operation mode that is desired for low power consumption devices. In contrast, gallium-rich oxides own relatively wider band gap, much lower carrier concentration and better stability due to the strong bonding between gallium and oxygen. Therefore, gallium ions are used as carrier density suppressor and to improve device stability.
High-performance metal-oxide semiconductors were initially obtained by sputtering that is currently widely used in industry. However, sputtering is an expensive technique and the substrate size is limited by the vacuum chamber. In addition, the film composition cannot be tuned at will because of the fixed composition of targets. In comparison, sol-gel process is an attractive alternative to produce metal-oxide semiconductors in a low-cost and scalable fashion. Additionally, sol-gel is advantageous for easy compositional tuning by choosing different precursors, solvents and additives. Nonetheless, device performance, in particular field-effect mobility and device stability, of metal-oxide semiconductors produced by sol-gel method has lagged behind those produced by sputtering.
Our multiple-layer-stacking method according to an embodiment of the current invention produces metal-oxide thin films with unique composition gradient and exhibits significantly improved device performance compared to metal-oxide thin films with uniform cation distribution. In our specific example, the key findings include:
1. The GZO/221/912 films show mobility much higher than pure 221 films and no less than pure 912 films.
TABLE I reports field-effect mobility of channel semiconductors shown in
The above results in Table I and
2. More importantly, with the high-gallium top layer, GZO/221/912 films are proven to be robust enough to survive plasma treatment.
The pure 221 or 912 films form a surface conductive layer after being treated with mild plasma and thus lose their transistor functionality. In contrast, GZO/221/912 film retain its transistor performance without noticeable shift in turn-on voltage after being treated with plasma, making it possible to deposit a layer of PECVD SiO2 as passivation layer to further improve the device stability.
3. The TFTs with GZO/221/912 film as channel semiconductor and passivated with PECVD SiO2 show significantly improved stability under long time positive gate bias stress (PBS) test, with a Von shift of 2.5 V under PBS of 20 V (2 MV/cm) for 10000 seconds (See
In comparison, devices with 221/912 channel show a Von shift of >10 V with the same PBS duration. We observed similar stability enhancement in Ga2O3/InZnO bilayer structured thin films (See,
Regardless of the specific example of GZO/221/912 films, our method can provide the following additional benefits:
1. Simplicity and versatility: In an embodiment, the method described herein is very simple to implement and easy to follow. Although GZO/221/912 film is used as an example, any precursor combination that can produce ion concentration gradient and/or bandgap variation along the thickness direction can be used, such as Ga2O3/In2O3, Ga2O3/ZnO, Ga2O3/InZnOx, GaZnOx/In2O3, GaZnOx/InZnOx, ZnO/SnO2, GaZnO/ZnO, GaZnO/SnO2, etc. It is also a universal strategy to combine multiple merits in one single system, whereas the metal-oxide semiconductors consisting of In, Ga and Zn are just one example. For example, multiferroic thin-films with similar content gradient may be realized by using materials that exhibit ferroelectric or ferromagnetic properties depending on their chemical compositions.
2. Low-cost and scalability: This method naturally inherits the merits of solution processes, i.e., being low-cost and easy for scalable fabrication. In this specific example, the GZO/221/912 films show device performance that is comparable with that of sputtered IGZO films, yet with much simpler deposition procedures, lower cost and no limit in substrate size.
3. Controllability: This method is especially useful when precise compositional control of sol-gel film is required. In ordinary solution processes, although the ratio of different metal ions in precursor solutions can be easily tuned by precisely controlling the amount of metal salts, harnessing the composition of the final metal-oxide thin-films has been challenging due to the mismatch in ion size, interaction with ligands and adhesion on substrate surface for different metal ions. As a result, the resulting sol-gel film usually has radically different composition than that expected by directly deriving from the precursor solution. In addition, content gradient cannot be controllably achieved by merely tuning the constituent concentration or ligand interaction in precursor solutions. In contrast, the method invented here can produce sol-gel films with desired compositions and composition distribution through the film thickness in a controllable manner.
In the embodiments shown in
The embodiments illustrated and discussed in this specification are intended only to teach those skilled in the art how to make and use the invention. In describing embodiments of the invention, specific terminology is employed for the sake of clarity. However, the invention is not intended to be limited to the specific terminology so selected. The above-described embodiments of the invention may be modified or varied, without departing from the invention, as appreciated by those skilled in the art in light of the above teachings. It is therefore to be understood that, within the scope of the claims and their equivalents, the invention may be practiced otherwise than as specifically described.
The present patent application claims priority benefit to U.S. provisional application No. 62/820,617, filed on Mar. 19, 2019, the entire content of which is incorporated herein by reference.
Number | Date | Country | |
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62820617 | Mar 2019 | US |