# Patent

## Title
Nickel complexes for flexible transistors and inverters

## Abstract

The design and synthesis of six nickel charge transfer (CT) complexes are described herein. The six nickel CT complexes have a nickel center, two organic ligands coordinated with the nickel center to form a dianionic square planar supramolecule and an organic counter-cation as represented by




The ligands and counter-cations are selected to optimize properties, such as molecular alignment, film morphology, and molecular packaging. Described herein, the ligands can be 2,3-pyrazinedithiol (L1), 1,2-benzenedithol (L2) or 2,3-quinoxalinedithol (L3) and the counter-cations can be diquat (2,2′-ebpy) or methyl viologen (4,4′-mbpy). The six nickel CT complexes can also be utilized semiconductor devices, such as thin film transistors or inverters. Processes are also provided for the fabrication of semiconductors devices. The processes can include fabricating a substrate with a bilayer octadecylphosphonic acid (ODPA)/Al2O3 dielectric and applying one of the six nickel charge transfer (CT) complexes to the substrate.

## Background
RELATED APPLICATION
The subject application is a divisional of, and claims priority to, U.S. patent application Ser. No. 13/097,656, filed Apr. 29, 2011, and entitled “NICKEL COMPLEXES FOR FLEXIBLE TRANSISTORS AND INVERTERS,” the entirety of which application is hereby incorporated by reference herein.


TECHNICAL FIELD
This disclosure generally relates to the development and synthesis of nickel complexes and the use of the nickel complexes in flexible thin film transistors and inverters.
BACKGROUND
Semiconductor devices, such as flexible thin film transistors (TFTs) and inverters, have been widely used in a variety of modern applications. Examples of these applications include, but are not limited to, liquid crystal displays, electronic paper, and radio frequency identification tags. There is a growing demand to make these applications less expensive and more efficient. This demand drives the development and synthesis of new semiconducting materials that can facilitate production of inexpensive and highly efficient semiconductor devices.
Over the last thirty years, inorganic based charge-transfer (CT) compounds with interesting physical and spectroscopic properties have been investigated as potential new semiconducting materials. One example of inorganic based CT compounds with interesting physical and spectroscopic properties are nickel-based CT complexes. Molecular alignment, film morphology and molecular packing of the nickel CT complexes make them inexpensive and highly efficient semiconductor materials.
Nickel has eight valence electrons in the 3d-orbital and, therefore, can intrinsically coordinate with two neutral organic ligands and form a dianionic square planar supramolecule. Accordingly, the molecular alignment, film morphology and molecular packing depend on the selection of the organic ligands and counter cations for the nickel CT complexes. The selection of the organic ligands and the counter cations influences molecular interactions, thereby influencing the molecular arrangement, film morphology, and molecular packing of the resulting bulk semiconducting materials. By proper selection of the organic ligands and the counter cations, efficiency of the semiconducting material can be increased.
The foregoing description is merely intended to provide an overview of some of the conventional semiconductor devices and semiconducting materials, and is not intended to be exhaustive. Problems with the state of the art and corresponding benefits of some of the various non-limiting embodiments may become further apparent upon review of the following detailed description.
SUMMARY
The following presents a simplified summary of the various embodiments in order to provide a basic understanding of some aspects described herein. This summary is not an extensive overview of the disclosed subject matter. It is intended to neither identify key or critical elements of the disclosed subject matter nor delineate the scope of the subject embodiments. Its sole purpose is to present some concepts of the disclosed subject matter in a simplified form as a prelude to the more detailed description that is presented later.
Various embodiments are directed to the design of semiconducting materials. The semiconducting materials can be nickel charge transfer (CT) complexes. The nickel CT complexes can include a nickel center, two neutral organic ligands coordinated with the nickel center to form a dianionic square planar supramolecule, and a counter-cation. The ligands and counter-cations are selected to optimize properties, such as molecular alignment, film morphology, and molecular packaging. For example, the ligands and/or counter cation can be chosen so that the nickel CT complex is self-assembling. Described herein, the ligands can be 2,3-pyrazinedithiol (L1), 1,2-benzenedithol (L2) or 2,3-quinoxalinedithol (L3) and the counter-cations can be diquat (2,2′-ebpy) or methyl viologen (4,4′-mbpy).
In another non-limiting embodiment, a process is provided for synthesizing the nickel CT complexes. The process can include dissolving a compound including a dianionic square planar complex of nickel and two organic neutral ligands with a nickel center and a compound including a counter-cation in a solvent. The process can also include precipitating the nickel CT complex including the dianionic square planar complex of nickel and two organic nickel ligands and the counter-cation. Described herein, the ligands can be 2,3-pyrazinedithiol (L1), 1,2-benzenedithol (L2) or 2,3-quinoxalinedithol (L3) and the counter-cations can be diquat (2,2′-ebpy) or methyl viologen (4,4′-mbpy).
The nickel CT complexes can also be semiconductor devices, such as thin film transistors or inverters. The thin film transistors or inverters can be used in connection with radio frequency identification (RFID) tag systems. The RFID tag can be a low frequency RFID tag.
Processes are also provided for the fabrication of semiconductors devices. The processes can include fabricating a substrate with a bilayer octadecylphosphonic acid (ODPA)/Al2O3 dielectric. The bilayer can be formed at a low temperature, for example, at room temperature. The processes can further include applying one of the six nickel charge transfer (CT) complexes to the substrate, for example, by spin coating.
The following description and the annexed drawings set forth in detail certain illustrative aspects of the disclosed subject matter. These aspects are indicative, however, of but a few of the various ways in which the principles of the various embodiments may be employed. The disclosed subject matter is intended to include all such aspects and their equivalents. Other advantages and distinctive features of the disclosed subject matter will become apparent from the following detailed description of the various embodiments when considered in conjunction with the drawings.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic process flow diagram of a process for synthesizing a nickel charge transfer complex.
FIG. 2 is a schematic process flow diagram of a process for synthesizing a nickel charge transfer complex with a ligand 2,3-pyrazinedithiol (L1) and a counter-cation diquat (2,2′-ebpy).
FIG. 3 is a schematic process flow diagram of a process for synthesizing a nickel charge transfer complex with a ligand 2,3-pyrazinedithiol (L1) and a counter-cation methyl viologen (4,4′-mbpy).
FIG. 4 is a schematic process flow diagram of a process for synthesizing a nickel charge transfer complex with a ligand 1,2-benzenedithol (L2) and a counter-cation diquat (2,2′-ebpy).
FIG. 5 is a schematic process flow diagram of a process for synthesizing a nickel charge transfer complex with a ligand 1,2-benzenedithol (L2) and a counter-cation methyl viologen (4,4′-mbpy).
FIG. 6 is a schematic process flow diagram of a process for synthesizing a nickel charge transfer complex with a ligand 2,3-quinoxalinedithol (L3) and a counter-cation diquat (2,2′-ebpy).
FIG. 7 is a schematic process flow diagram of a process for synthesizing a nickel charge transfer complex with a ligand 2,3-quinoxalinedithol (L3) and a counter-cation methyl viologen (4,4′-mbpy).
FIG. 8 shows a scanning electron microscopy (SEM) images and a grazing incidence X-ray powered diffraction (GIXRD) spectrum of a nickel CT complexes.
FIG. 9 is a schematic process flow diagram of a process for fabricating a substrate fir a semiconductor device.
FIG. 10 shows the suitability of thin films produced using the process shown in FIG. 9 for fabricating semiconductor devices.
FIG. 11 is a schematic process flow diagram of a method for fabricating a semiconductor device with a nickel CT complex.
FIG. 12 is a schematic illustration of an as-fabricated patterned substrate.
FIG. 13 shows a plot of the output characteristics of the [2,2′-ebpy][Ni(L2)2]2— based thin film field-effect transistor.
FIG. 14 shows a scanning electron microscopy (SEM) image and a grazing incidence X-ray powered diffraction (GIXRD) spectrum of a nickel CT complex.
FIG. 15 shows a scanning electron microscopy (SEM) image and a grazing incidence X-ray powered diffraction (GIXRD) spectrum of a nickel CT complex.
FIG. 16 shows a scanning electron microscopy (SEM) image and a grazing incidence X-ray powered diffraction (GIXRD) spectrum of a nickel CT complex.
FIG. 17 shows a scanning electron microscopy (SEM) image and a grazing incidence X-ray powered diffraction (GIXRD) spectrum of a nickel CT complex.
FIG. 18 shows a scanning electron microscopy (SEM) image and a grazing incidence X-ray powered diffraction (GIXRD) spectrum of a nickel CT complex.



DETAILED DESCRIPTION
Various aspects relate to the development of nickel charge transfer (CT) complexes for semiconductor device applications (e.g., flexible thin film transistors (TFTs) and inverters. A nickel CT complex includes a nickel center, two organic ligands, and a counter-cation. Selection of the organic ligands and the counter-cation can influence the material properties of the nickel CT complex and, therefore, the suitability of the nickel CT complex for high performance semiconductor device applications (e.g., applications requiring a high efficiency).
The nickel has eight valence electrons in the 3d-orbital, which allows the nickel to intrinsically coordinate with two neutral organic ligands. This coordination between the nickel center and the two neutral organic ligands can lead to dianionic square planar supramolecule. The ligand and counter-cation can influence properties of the nickel CT complex, including molecular alignment, film morphology and molecular packing.
Referring now to FIG. 1, illustrated is a schematic process flow diagram showing a process 100 for synthesizing a nickel CT complex. At element 102, a ligand and a counter-cation can be chosen for the nickel CT complex. For example, the ligand can be a neutral organic ligand that can coordinate with the nickel. For another example, the counter cation can be an organic cation. The ligand and the CT complex can be chosen to optimize properties of the nickel CT complex, such as molecular alignment, film morphology, and molecular packaging, to create an efficient, inexpensive semiconductor device.
At element 104, the nickel and two ligands can coordinate to form a molecule with nickel as the center. The molecule can be a dianionic square planar supramolecule. At element 106, an ionic complex containing the nickel and two ligands and an ionic complex containing the counter-cation can be dissolved in a solvent. At element 108, the solution can be stirred (and, optionally, heated), allowing a precipitate to form. At element 110, the precipitate can be collected and processed (e.g., filtered, washed, and/or dried). The processed precipitate is the nickel CT complex.
Properties of the resulting nickel CT complex, such as molecular alignment, film morphology, and molecular packing, can be influenced by the selection of the ligand and a counter-cation. Described herein is the design and synthesis of six such square planar nickel CT complexes with different combinations of organic ligands and counter-cations and the application of these six nickel CT complexes in semiconductor devices and electronic applications. The organic ligands described herein are L1, 2,3-pyrazinedithiol, L2, 1,2-benzenedithol, and L3, 2,3-quinoxalinedithol. The counter-cations described herein are [2,2′-ebpy], diquat, and [4,4′-mbpy], methyl viologen.
Selection of a different organic ligand and a different counter-cation for each of the six nickel CT complexes leads to differences in properties, such as molecular alignment, film morphology, and molecular packing of the bulk semiconducting material. Molecular alignment is a key issue for constructing a highly efficient semiconductor device. Film morphology and molecular packing are fundamental factors affecting carrier mobility of a given semiconductor. The ligands and counter-cations for the nickel CT complexes are selected so that the molecular alignment, film morphology, and molecular packing of the six nickel CT complexes can facilitate efficient semiconductor devices.
In one embodiment, the square planar nickel CT complex is [2,2′-ebpy][Ni(L1)2], where L1 is the organic ligand 2,3-pyrazinedithiol and [2,2′-ebpy] is the counter-cation diquat. The structure of [2,2′-ebpy][Ni(L1)2] is shown in formula (1).




Referring now to FIG. 2, illustrated therein is a schematic process flow diagram of a process 200 for synthesizing [2,2′-ebpy][Ni(L1)2]. At element 202, a complex including Ni(L1)2 and a complex including 2,2′-ebpy are dissolved in solvent (e.g., an organic solvent, such as an alcohol).
The complex including Ni(L1)2 can be Na2[Ni(L1)2]. For example, the Na2[Ni(L1)2] can be formed through the following process. L1 (2,3-pyrazinedithiol) and sodium metal can be dissolved in an organic solvent (e.g., methanol). For example, 3 g (20.8 mmol) of L1 and 5 g (201.8 mmol) of sodium metal can be added to 200 ml of methanol. The mixture can be stirred at room temperature until all of the solids are dissolved, for example, under nitrogen for 1 hour. Nickel(II) chloride hexahydrate (e.g., obtained from Sigma-Aldrich) can be added to the mixture of L1 and sodium metal. For example, 1.80 g (7.6 mmol) of nickel(II) chloride hexahydrate can be added in a dropwise manner to the mixture over a period of 30 minutes. The reaction mixture can be stirred at room temperature (e.g., under nitrogen for 3 hours). The resulting solution can have a reddish orange color. The solution can be filtered, and the collected filtrate evaporated. The solid collected can be washed with diethyl ether. This solid is Na2[Ni(L1)2]. According to an experimental preparation, 2.0 g of Na2[Ni(L1)2] were synthesized (yield 68%). Through elemental analysis: analytically, the Na2[Ni(L1)2] was predicted to have C: 62.11; H: 8.69; and N, 9.05; after the synthesis, Na2[Ni(L1)2] was found to have C: 62.02; H: 8.72; and N: 9.11. Utilizing mass spectroscopy, using an ESI-MS, −ve mode, and [M+Na)− was found to be m/z 364.9.
The complex including 2,2′-ebpy can be [(2,2′-ebpy)Br2]. The organic solvent in which the Na2[Ni(L1)2] and the [(2,2′-ebpy)Br2] can be dissolved can be methanol. For example, 2.2 g (5.6 mmol) of Na2[Ni(L1)2] and 18.7 g (54.3 mmol) of [(2,2′-ebpy)Br2] can be dissolved in 20 ml of methanol.
At element 204, the solution containing the dissolved Ni(L1)2 and 2,2′-ebpy can be heated under stirring. For example, the solution can be heated at 60° C. for 1 hour under stirring. During the heating and stirring, a precipitate can form. For example, the precipitate can be a black precipitate. At element 206, the precipitate can be filtered, collected, and processed. The processing can include washing (e.g., with methanol) and drying the precipitate.
According to an experimental preparation, 2.1 g of [2,2′-ebpy][Ni(L1)2] were synthesized (yield 70%). Through elemental analysis: analytically, the [2,2′-ebpy][Ni(L1)2] was predicted to have C: 45.55; H: 3.06; and N: 15.94 and after the synthesis, [2,2′-ebpy][Ni(L1)2] was found to have C: 45.40; H: 3.10; and N: 15.90. Utilizing mass spectroscopy, the nickel CT compound was analyzed, using an ESI-MS, −ve mode, [M]2− was found to be m/z 171.0 and utilizing +ve mode, 2,2′-ebpy]2+ was found to be m/z 92.1 [.
In another embodiment, the square planar nickel CT complex is [4,4′-mbpy][Ni(L1)2], where L1 is the organic ligand 2,3-pyrazinedithiol and [4,4′-mbpy] is the counter-cation methyl viologen. The structure of [4,4′-mbpy][Ni(L1)2] is shown in formula (2).




Referring now to FIG. 3, illustrated therein is a schematic process flow diagram of a process 300 for synthesizing [4,4′-mbpy][Ni(L1)2]. At element 302, a complex including Ni(L1)2 and a complex including 4,4′-ebpy are dissolved in solvent.
The complex including Ni(L1)2 can be Na2[Ni(L1)2]. For example, the Na2[Ni(L1)2] can be formed through the following process. L1 (2,3-pyrazinedithiol) and sodium metal can be dissolved in an organic solvent (e.g., methanol). For example, 3 g (20.8 mmol) of L1 and 5 g (201.8 mmol) of sodium metal can be added to 200 ml of methanol. The mixture can be stirred at room temperature until all of the solids are dissolved, for example, under nitrogen for 1 hour. Nickel(II) chloride hexahydrate can be added to the mixture of L1 and sodium metal. For example, 1.80 g (7.6 mmol) of nickel(II) chloride hexahydrate can be added in a dropwise manner to the mixture over a period of 30 minutes. The reaction mixture can be stirred at room temperature (e.g., under nitrogen for 3 hours). The resulting solution can have a reddish orange color. The solution can be filtered, and the collected filtrate evaporated. The solid collected can be washed with diethyl ether. This solid is Na2[Ni(L1)2]. According to an experimental preparation, 2.0 g of Na2[Ni(L1)2] were synthesized (yield 68%). Through elemental analysis: analytically, the Na2[Ni(L1)2] was predicted to have C: 62.11; H: 8.69; and N: 9.05; after the synthesis, Na2[Ni(L1)2] was found to have C: 62.02; H: 8.72; and N: 9.11. Utilizing mass-spectroscopy, using an ESI-MS, −ve mode, and [M+Na]− was found to be m/z 364.9.
The complex including 4,4′-ebpy can be [(4,4′-mbpy)I2]. The solvent in which the Na2[Ni(L1)2] and the [(4,4′-mbpy)I2] can be dissolved can be a water (e.g., hot water) and MeOH solution. For example, 1.7 g (1.3 mmol) of Na2[Ni(L1)2] and 9.5 g (21.5 mmol) of [(4,4′-mbpy)I2] can be dissolved in 140 ml of hot water/MeOH solution.
At element 304, the mixture containing the dissolved Ni(L1)2 and 4,4′-mbpy can be heated under stirring. For example, the solution can be heated at 60° C. for 1 hour under stirring. During the heating and stirring, a precipitate can form. For example, the precipitate can be a black precipitate. At element 306, the precipitate can be filtered, collected, and processed. The processing can include washing (e.g., with methanol) and drying the precipitate. The precipitate is insoluble in most common solvents.
According to an experimental preparation, 2.2 g of [4,4′-mbpy][Ni(L1)2] were synthesized (yield 95%). Through elemental analysis: analytically, the [4,4′-mbpy][Ni(L1)2] was predicted to have C: 45.38; H: 3.43; and N: 15.88. After the synthesis, [4,4′-mbpy][Ni(L1)2] was found to have C: 45.12; H: 3.51; and N: 15.92. Utilizing mass-spectroscopy, the nickel CT complex was analysed using an ESI-MS, −ve mode, and [M]− was found to be m/z 338.1.
In yet another embodiment, the square planar nickel CT complex is [2,2′-ebpy][Ni(L2)2], where L2 is the organic ligand 1,2-benzenedithol and [2,2′-ebpy] is the counter cation diquat. The structure of [2,2′-ebpy][Ni(L2)2] is shown in formula (3).




Referring now to FIG. 4, illustrated therein is a schematic process flow diagram of a process 400 for synthesizing [2,2′-ebpy][Ni(L2)2]. At element 402, a complex including Ni(L2)2 and a complex including 2,2′-ebpy are dissolved in solvent (e.g., an organic solvent, such as an alcohol).
The complex including Ni(L2)2 can be Na2[Ni(L2)2]. For example, the Na2[Ni(L2)2] can be formed through the following process. L2 (1,2-benzenedithol) and sodium metal can be dissolved in an organic solvent (e.g., methanol). For example, 2.5 g (17.6 mmol) of L2 and 5 g (200 mmol) of sodium metal can be added to 200 ml of methanol. The mixture can be stirred at room temperature until all of the solids are dissolved, for example, under nitrogen for 1 hour. Nickel(II) chloride hexahydrate can be added to the mixture of L2 and sodium metal. For example, 1.66 g (6.7 mmol) of nickel(II) chloride hexahydrate can be added in a dropwise manner to the mixture over a period of 30 minutes. The reaction mixture can be stirred at room temperature (e.g., under nitrogen for 3 hours). The resulting solution can have a reddish brown color. The solution can be filtered, and the collected filtrate evaporated. The solid collected can be washed with diethyl ether. This solid is Na2[Ni(L2)2]. According to an experimental preparation, 3.4 g of Na2[Ni(L2)2] were synthesized (yield 50%). Through elemental analysis: analytically, the Na2[Ni(L2)2] was predicted to have C: 39.80 and H: 2.23; after the synthesis, Na2[Ni(L2)2] was found to have C: 39.90 and H: 2.24. Utilizing mass-spectroscopy, using an ESI-MS, −ve mode, [M]− was found to be m/z 338.1.
The complex including 2,2′-ebpy can be [(2,2′-ebpy)Br2]. The organic solvent in which the Na2[Ni(L2)2] and the [(2,2′-ebpy)Br2] can be dissolved can be methanol. For example, 2.2 g (6.1 mmol) of Na2[Ni(L2)2] and 10 g (29.1 mmol) of [(2,2′-ebpy)Br2] can be dissolved in 200 ml of methanol.
At element 404, the solution containing the dissolved Ni(L2)2 and 2,2′-ebpy can be heated under stirring. For example, the solution can be heated at 60° C. for 1 hour under stirring. During the heating and stirring, a precipitate can form. For example, the precipitate can be a black precipitate. At element 406, the precipitate can be filtered, collected, and processed. The processing can include washing (e.g., with methanol) and drying the precipitate.
According to an experimental preparation, 1.3 g of [2,2′-ebpy][Ni(L1)2] were synthesized (yield 24%). Through elemental analysis: analytically, the [2,2′-ebpy][Ni(L2)2] was predicted to have C: 50.13; H: 3.27; and N: 3.25. After the synthesis, [2,2′-ebpy][Ni(L1)2] was found to have C: 50.21; H: 3.25; and N: 3.20. Utilizing mass-spectroscopy the nickel CT compound was analyzed, using an ESI-MS, −ve mode, [M]− was found to be m/z 338.1 and utilizing +ve mode, [2,2′-ebpy]2+ was found to be m/z 92.1.
In a further embodiment, the square planar nickel CT complex is [4,4′-mbpy][Ni(L2)2], where L2 is the organic ligand 1,2-benzenedithol and [4,4′-mbpy] is the counter-cation methyl viologen. The structure of [4,4′-mbpy][Ni(L2)2] is shown in formula (4).




Referring now to FIG. 5, illustrated therein is a schematic process flow diagram of a process 500 for synthesizing [4,4′-mbpy][Ni(L2)2]. At element 502, a complex including Ni(L2)2 and a complex including 4,4′-ebpy are dissolved in solvent.
The complex including Ni(L2)2 can be Na2[Ni(L2)2]. For example, the Na2[Ni(L2)2] can be formed through the following process. L2 (1,2-benzenedithol) and sodium metal can be dissolved in an organic solvent (e.g., methanol). For example, 2.5 g (17.6 mmol) of L2 and 5 g (200 mmol) of sodium metal can be added to 200 ml of methanol. The mixture can be stirred at room temperature until all of the solids are dissolved, for example, under nitrogen for 1 hour. Nickel(II) chloride hexahydrate can be added to the mixture of L2 and sodium metal. For example, 1.66 g (6.7 mmol) of nickel(II) chloride hexahydrate can be added in a dropwise manner to the mixture over a period of 30 minutes. The reaction mixture can be stirred at room temperature (e.g., under nitrogen for 3 hours). The resulting solution can have a reddish brown color. The solution can be filtered, and the collected filtrate evaporated. The solid collected can be washed with diethyl ether. This solid is Na2[Ni(L2)2]. According to an experimental preparation, 3.4 g of Na2[Ni(L2)2] were synthesized (yield 50%). Through elemental analysis: analytically, the Na2[Ni(L2)2] was predicted to have C: 39.80 and H: 2.23; after the synthesis, Na2[Ni(L2)2] was found to have C: 39.90 and H: 2.24. Utilizing mass-spectroscopy, using an ESI-MS, −ve mode, [M]− was found to be m/z 338.1.
The complex including 4,4′-ebpy can be [(4,4′-mbpy)I2]. The solvent in which the Na2[Ni(L2)2] and the [(4,4′-mbpy)I2] can be dissolved can be a water (e.g., hot water) and MeOH solution. For example, 1.7 g (4.7 mmol) of Na2[Ni(L2)2] and 10 g (22.7 mmol) of [(4,4′-mbpy)I2] can be dissolved in 14 ml of hot water/MeOH solution (2:5 v/v).
At element 504, the mixture containing the dissolved Ni(L2)2 and 4,4′-mbpy can be heated under stirring. For example, the solution can be heated at 60° C. for 1 hour under stirring. During the heating and stirring, a precipitate can form. For example, the precipitate can be a black precipitate. At element 506, the precipitate can be filtered, collected, and processed. The processing can include washing (e.g., with a hot water/methanol mixture) and drying the precipitate.
According to an experimental preparation, 2.9 g of [4,4′-mbpy][Ni(L2)2] were synthesized (yield 75%). Through elemental analysis: analytically, the [4,4′-mbpy][Ni(L2)2] was predicted to have C: 50.01; H: 3.50; and N: 3.24 and after the synthesis, [4,4′-mbpy][Ni(L1/2)2] was found to have C: 50.08; H: 3.45; and N: 3.19. Utilizing mass-spectroscopy, the nickel CT complex was analysed using an ESI-MS, −ve mode, [M] was found to be m/z 338.1 and utilizing +ve mode, [4,4′-mbpy]2+ was found to be m/z 93.2.
In yet a further embodiment, the square planar nickel CT complex is [2,2′-ebpy][Ni(L3)2], where L3 is the organic ligand 2,3-quinoxalinedithol and [2,2′-ebpy] is the counter-cation diquat. The structure of [2,2′-ebpy][Ni(L3)2] is shown in formula (5).




Referring now to FIG. 6, illustrated therein is a schematic process flow diagram of a process 600 for synthesizing [2,2′-ebpy][Ni(L3)2]. At element 602, a complex including Ni(L3)2 and a complex including 2,2′-ebpy are dissolved in solvent (e.g., an organic solvent, such as an alcohol).
The complex including Ni(L3)2 can be Na2[Ni(L3)2]. For example, the Na2[Ni(L3)2] can be formed through the following process. L3 (2,3-quinoxalinedithol) and sodium metal can be dissolved in an organic solvent (e.g., methanol). For example, 2.5 g (12.9 mmol) of L3 and 3 g (130 mmol) of sodium metal can be added to 200 ml of methanol. The mixture can be stirred at room temperature until all of the solids are dissolved, for example, under nitrogen for 1 hour. Nickel(II) chloride hexahydrate dissolved in a 300 ml methanol can be added to the mixture of L3 and sodium metal. For example, 1.03 g (4.3 mmol) of nickel(II) chloride hexahydrate can be added in a dropwise manner to the mixture over a period of 30 minutes. The reaction mixture can be stirred at room temperature (e.g., under nitrogen for 3 hours). The resulting solution can have a dark red, clear color. The solution can be filtered, and the collected filtrate evaporated. The solid collected can be washed with diethyl ether. This solid is Na2[Ni(L3)2]. According to an experimental preparation, 3.2 g of Na2[Ni(L3)2] were synthesized (yield 50%). Through elemental analysis: analytically, the Na2[Ni(L3)2] was predicted to have C: 39.28; H: 1.65; and N: 11.45; after the synthesis, Na2[Ni(L3)2] was found to have C: 39.12; H: 1.71; and N: 11.39. Through proton nuclear magnetic resonance (1H NMR) (d-DMSO3): 7.43 (m, 4H), 7.19 (m, 4H). Utilizing mass-spectroscopy, using an ESI-MS, −ve mode, [M+Na]− was found to be m/z 465.1.
The complex including 2,2′-ebpy can be [(2,2′-ebpy)Br2]. The organic solvent in which the Na2[Ni(L3)2] and the [(2,2′-ebpy)Br2] can be dissolved can be methanol. For example, 1.3 g (2.7 mmol) of Na2[Ni(L3)2] and 10 g (29.1 mmol) of [(2,2′-ebpy)Br2] can be dissolved in 200 ml of methanol.
At element 604, the solution containing the dissolved Ni(L3)2 and 2,2′-ebpy can be heated under stirring. For example, the solution can be heated at 60° C. for 4 hour under stirring. During the heating and stirring, a precipitate can form. At element 606, the precipitate can be filtered, collected, and processed. The processing can include washing (e.g., with methanol) and drying the precipitate.
According to an experimental preparation, 2.4 g of [2,2′-ebpy][Ni(L3)2] were synthesized (yield 65%). Through elemental analysis: analytically, the [2,2′-ebpy][Ni(L3)2] was predicted to have C: 53.60; H: 3.21; and N: 13.39 and after the synthesis, [2,2′-ebpy][Ni(L3)2] was found to have C: 53.84; H: 3.22; and N: 13.29. Through proton nuclear magnetic resonance (1H NMR) (d-DMSO3): 9.27 (d, 2H, J=6.8 Hz), 9.06 (d, 2H, J=8.0 Hz), 8.82 (t, 2H, J=8.0 Hz), 8.31 (t, 2H, J=6.8 Hz), 7.41 (m, 4H), 7.19 (m, 4H), 5.30 (s, 4H). Utilizing mass-spectroscopy, the nickel CT complex was analyzed using an ESI-MS, −ve mode, and [M+H]− was found to be m/z 443.0 and utilizing +ve mode [2,2′-ebpy]2+ was found to be m/z 92.1.
In another embodiment, the square planar nickel CT complex is [4,4′-mbpy][Ni(L3)2], where L3 is the organic ligand 2,3-quinoxalinedithol and [4,4′-mbpy] is the counter-cation methyl viologen. The structure of [4,4′-mbpy][Ni(L3)2] is shown in formula (6).




Referring now to FIG. 7, illustrated therein is a schematic process flow diagram of a process 700 for synthesizing [4,4′-mbpy][Ni(L3)2]. At element 702, a complex including Ni(L3)2 and a complex including 4,4′-ebpy are dissolved in solvent.
The complex including Ni(L3)2 can be Na2[Ni(L3)2]. For example, the Na2[Ni(L3)2] can be formed through the following process. L3 (2,3-quinoxalinedithol) and sodium metal can be dissolved in an organic solvent (e.g., methanol). For example, 2.5 g (12.9 mmol) of L3 and 3 g (130 mmol) of sodium metal can be added to 200 ml of methanol. The mixture can be stirred at room temperature until all of the solids are dissolved, for example, under nitrogen for 1 hour. Nickel(II) chloride hexahydrate dissolved in a 300 ml methanol can be added to the mixture of L3 and sodium metal. For example, 1.03 g (4.3 mmol) of nickel(II) chloride hexahydrate can be added in a dropwise manner to the mixture over a period of 30 minutes. The reaction mixture can be stirred at room temperature (e.g., under nitrogen for 3 hours). The resulting solution can have a dark red, clear color. The solution can be filtered, and the collected filtrate evaporated. The solid collected can be washed with diethyl ether. This solid is Na2[Ni(L3)2]. According to an experimental preparation, 3.2 g of Na2[Ni(L3)2] were synthesized (yield 50%). According to an experimental preparation, 3.2 g of Na2[Ni(L3)2] were synthesized (yield 50%). Through elemental analysis: analytically, the Na2[Ni(L3)2] was predicted to have C: 39.28; H: 1.65; and N: 11.45; after the synthesis, Na2[Ni(L3)2] was found to have C: 39.12; H: 1.71; and N: 11.39. Through proton nuclear magnetic resonance (1H NMR) (d-DMSO3): 7.43 (m, 4H), 7.19 (m, 4H). Utilizing mass-spectroscopy, using an ESI-MS, −ve mode, was found to be [M+Na]− m/z 465.1.
The complex including 4,4′-ebpy can be [(4,4′-mbpy)I2]. The solvent in which the Na2[Ni(L2)2] and the [(4,4′-mbpy)I2] can be dissolved can be a methanol solution. For example, 1.3 g (2.7 mmol) of Na2[Ni(L3)2] and 10 g (22.7 mmol) of [(4,4′-mbpy)I2] can be dissolved in 200 ml of methanol.
At element 704, the mixture containing the dissolved Ni(L3)2 and 4,4′-mbpy can be heated under stirring. For example, the solution can be heated at 60° C. for 4 hours under stirring. During the heating and stirring, a precipitate can form. At element 706, the precipitate can be filtered, collected, and processed. The processing can include washing (e.g., with methanol) and drying the precipitate.
According to an experimental preparation, 2.1 g of [4,4′-mbpy][Ni(L3)2] were synthesized (yield 75%). Through elemental analysis: analytically, the [4,4′-mbpy][Ni(L3)2] was predicted to have C: 53.43; H: 3.52; and N: 13.35. and after the synthesis, [4,4′-mbpy][Ni(L3)2] was found to have C: 53.21; H: 3.57; and N: 13.41. Through proton nuclear magnetic resonance (1H NMR) (d-DMSO): 9.19 (d, 4H, J=6.8 Hz), 8.66 (d, 4H, J=6.8 Hz), 7.43 (m, 4H), 7.21 (m, 4H), 4.38 (s, 4H). Utilizing mass-spectroscopy, the nickel CT complex was analysed using an ESI-MS, −ve mode, [M]2− was found to be m/z 220.5 and utilizing +ve mode, [4,4′-mbpy]2+ was found to be m/z 93.2.
The six nickel CT complexes, 2,2′-ebpy][Ni(L1)2], [4,4′-mbpy][Ni(L1)2], [2,2′-ebpy][Ni(L2)2], [4,4′-mbpy][Ni(L2)2], [2,2′-ebpy][Ni(L3)2] and [4,4′-mbpy][Ni(L3)2], have favorable properties to traditional nickel CT complexes. For example, the six nickel CT complexes are more thermally stable than traditional nickel CT complexes.
Thermal stabilities for the six nickel CT complexes, [2,2′-ebpy][Ni(L1)2], [4,4′-mbpy][Ni(L1)2], [2,2′-ebpy][Ni(L2)2], [4,4′-mbpy][Ni(L2)2], [2,2′-ebpy][Ni(L3)2] and [4,4′-mbpy][Ni(L3)2], can be exhibited, for example, according to decomposition temperatures. As shown in TABLE 1, the decomposition temperatures for the six nickel CT complexes, [2,2′-ebpy][Ni(L1)2], [4,4′-mbpy][Ni(L1)2], [2,2′-ebpy][Ni(L2)2], [4,4′-mbpy][Ni(L2)2], [2,2′-ebpy][Ni(L3)2] and [4,4′-mbpy][Ni(L3)2], were tested against the decomposition temperatures of traditional nickel CT complexes, Na2[Ni(L1)2], Na2[Ni(L2)2], and Na2[Ni(L3)2]. Each of the six nickel CT complexes, [2,2′-ebpy][Ni(L1)2], [4,4′-mbpy][Ni(L1)2], [2,2′-ebpy][Ni(L2)2], [4,4′-mbpy][Ni(L2)2], [2,2′-ebpy][Ni(L3)2] and [4,4′-mbpy][Ni(L3)2], exhibited a higher decomposition temperature than traditional nickel CT complexes Na2[Ni(L1)2], Na2[Ni(L2)2], and Na2[Ni(L3)2]. The three nickel CT complexes with the counter-cation methyl viologen, [4,4′-mbpy][Ni(L1)2], [4,4′-mbpy][Ni(L2)2], and [4,4′-mbpy][Ni(L3)2] are more thermally stable than both traditional nickel CT complexes, Na2[Ni(L1)2], Na2[Ni(L2)2], and Na2[Ni(L3)2], and nickel CT complexes with the counter-cation diquat, [2,2′-ebpy][Ni(L1)2], [2,2′-ebpy][Ni(L2)2], and [2,2′-ebpy][Ni(L3)2].













Tdecomp/° C.[a]



















Na2[Ni(L1)2]
200



[2,2′-ebpy][Ni(L1)2]
275



[4,4′-mbpy] [Ni(L1)2]
290



Na2[Ni(L2)2]
200



[2,2′-ebpy][Ni(L2)2]
250



[4,4′-mbpy] [Ni(L2)2]
250



Na2[Ni(L3)2]
210



[2,2′-ebpy][Ni(L3)2]
210



[4,4′-mbpy] [Ni(L3)2]
300










TABLE 1: Decomposition temperature of the six nickel CT complexes. [a] Temperature of 10% weight loss utilizing a thermogravimetry analyzer (TA Instruments) Q5—from 30 to 100° C. at a heating rate of 10° C./min under N2 atmosphere.

Further for example, the six nickel CT complexes exhibit favorable properties including molecular alignment, film morphology and molecular packaging. Molecular alignment is a key issue for constructing highly efficient organic semiconductor devices. Film morphology and molecular packaging are fundamental factors affecting carrier mobility of a given semiconductor.
Referring now to FIGS. 8, and 14-18, illustrated are scanning electron microscopy (SEM) images and grazing incidence X-ray powered diffractions (GIXRD) spectra of thin films of the six nickel CT complexes. Surface image of thin films of the six nickel CT complexes were recorded by Philips XL30 FEG SEM. GIXRD were recorded using a Bruker D8 Advance diffractometer with a CuKα X-ray radiation (λ=1.54146 Å, rated at 1.6 kW) with scan range=1.5-30° (2θ), step size=0.05°, scan speed=1 s per step.
The three nickel CT complexes with counter-cation diquat, [2,2′-ebpy][Ni(L1)2](SEM 802, GIXRD 804), [2,2′-ebpy][Ni(L2)2](SEM 806, GIXRD 808), [2,2′-ebpy][Ni(L3)2](SEM 810, GIXRD 812), exhibit a smooth film morphology with an amorphous nature. The three nickel CT complexes with the counter-cation methyl viologen, [4,4′-mbpy][Ni(L1)2](SEM 814, GIXRD 816), [4,4′-mbpy][Ni(L2)2](SEM 818, GIXRD 820), [4,4′-mbpy][Ni(L3)2](SEM 822, GIXRD 824), exhibit regular rod morphology with crystallized properties.
Referring now to FIG. 9, illustrated is a schematic process flow diagram of a process 900 for fabricating a substrate for a semiconductor device (e.g., a thin film transistor or inverter). At element 902, a gate electrode can be deposited onto a substrate. For example, the gate electrode can be an Ag gate electrode. The Ag gate electrode can be a 50-nm thick Ag film. The substrate can be a poly(ethylene terephthalate) (PET) substrate (e.g., a flexible PET substrate). The gate electrode can be deposited onto the substrate, for example, through a shadow mask by thermal evaporation.
At element 904, a gate dielectric can be deposited on the gate electrode and substrate. For example, the gate dielectric can be an Al2O2 layer. The Al2O2 layer can be a patterned 26-nm thick Al2O2 layer. The gate dielectric can be deposited on the substrate (e.g., Ag/PET substrate) by, for example, a Savannah 100 ALD system at a substrate temperature of 80° C. and 1.8×10−1 Torr.
At element 906, an octadecylphosphonic acid (ODPA) self-assembled monolayer (SAM) can be applied to the substrate after fabricating the gate dielectric. The ODPA SAM can be prepared, for example, by immersing the substrate in a 2-propanol solution containing 5 mM of ODPA. Keeping the solution at room temperature, the substrates can remain in the solution for a time period. For example, the time period can be 17 hours. After the period in solution, the substrates can be rinsed (e.g., by pure 2-propanol), blown dry (e.g., with nitrogen), and briefly baked (e.g., on a hotplate at 60° C. for 30 minutes). Accordingly, the bilayer ODPA/Al2O3 can be processed at a low temperature on PET substrates.
Process 900 produces films substrates suitable for fabricating a semiconductor device, such as a low voltage thin film transistor. For example, the thin films can exhibit a stable capacitance between 20 Hz and 600 kHz. Performance and mechanical properties of ODPA/Al2O3 were found to be superior to both Al2O3 alone, as well as SiO2. FIG. 10 illustrates the suitability of the films produced using process 900 for fabricating a semiconductor device. Element (a) is a plot of current density versus electric field characteristics for Al2O3 and ODPA/Al2O3. For the ODPA/Al2O3, the leakage current density was fond to be 7×10−3 A/cm2 at an applied electrical field of 2 MV/cm. Element (b) is a plot of capacitance density (Cox) versus frequency characteristics for Al2O3 and ODPA/Al2O3. The capacitance density for ODPA/Al2O3 was shown to be  ̃172 nF/cm2. Element (c) is a capacitor model for Al2O3 and bilayer ODPA/Al2O3. Element (d) is a 3D tapping mode atomic force microscopy (AFM) height image of Al2O3. Element (e) is a 3D tapping mode AFM height image of a bilayer ODPA/Al2O3.
The bilayer ODPA/Al2O3 can be formed at a low temperature on the flexible substrate for device fabrication. In semiconductor devices, this bilayer dielectric can help to enhance the mobility of the six nickel CT complexes in semiconductor device applications. This can lead to an improved performance of the semiconductor devices (e.g., high performance, flexible, and/or operational at low voltages ( ̃3V)).
Referring now to FIG. 11, illustrated is a schematic process flow diagram of a process 1100 for fabricating a semiconductor device utilizing one of the six nickel CT complexes. At element 1102, source/drain contact patterns can be formed on a flexible PET substrate. The source/drain patterns can be, for example, Au source/drain contact patterns. The source/drain patterns can be formed via shadow mask. The substrate can be, for example, an flexible ODPA/Al2O3/PET substrate as described with respect to FIGS. 9 and 10. An example of a patterned substrate fabricated according to element 1102 is shown in FIG. 12.
Referring back to FIG. 11, at element 1104, a nickel CT complex can be dissolved. For example, the nickel CT complex can be [2,2′-ebpy][Ni(L1)2], [4,4′-mbpy][Ni(L1)2], [2,2′-ebpy][Ni(L2)2], [4,4′-mbpy][Ni(L2)2], [2,2′-ebpy][Ni(L3)2] and [4,4′-mbpy][Ni(L3)2]. The nickel CT complex can be dissolved in dimethylformamide (DMF). For example, the nickel CT complex can be dissolved in the DFM by ultrasonic bath.
At element 1106, the resulting solution can be spin coated on the patterned substrates (e.g., patterned ODPA/Al2O3/PET substrates). The solution can be spin coated with a spin speed of 2000 rmp/min. At element 1108, the coated pattern substrate can be annealed. For example, the coated patterned substrate can be annealed at 100° C. under N2 atmosphere for 20 minutes.
For example, at element 1104, [2,2′-ebpy][Ni(L2)2]2 can be dissolved in DMF and, at element 1106, spin coated on a patterned ODPA/Al2O3/PET substrate. The output, transfer and transient characteristics of the as-fabricated [2,2′-ebpy][Ni(L2)2]2 thin film field-effect transistor were measured inside a N2 glove box (Mbraun MB20G) equipped with a probe station connected to a semiconductor parameter analyzer (Keithley 4200 SCS). FIG. 13 shows a plot of the output characteristics of the [2,2′-ebpy][Ni(L2)2]2—based thin film field-effect transistor. The [2,2′-ebpy][Ni(L2)2]2 thin film field-effect transistor exhibits both electron and hole properties. The field-effect charge mobility (μ) can be estimated from the output characteristics in the saturation region or linear region and was estimated as up to 0.1 cm2/Vs (channel length is 50 m and channel width is 1000 μm).
The six nickel CT complexes have superior electrical properties to other CT complexes. The six nickel CT complexes provide comparatively high carrier mobility with respect to traditional nickel CT complexes. Through selection of the organic ligand and/or the organic counter-cation, the six nickel CT complexes are able to self-assemble in the active layer of semiconducting devices. This can increase the carrier concentration in the conduction band and, accordingly, provide high carrier mobility. Self-assembly has been previously shown with other organic-based CT complexes to increase carrier mobility. For example, charged cationic cyclometalated iridium(III) polypyridine complexes were electrostatically aligned in order for enhancing the carrier mobility; likewise self-assembled DNA nucleosides was used to fabricate high efficient hybrid molecular devices. The conductive properties of these devices are greatly influenced by their aligned structures, since the amorphous structure of those materials are behaved as insulators. In the six nickel CT complexes the organic ligand and/or the organic counter-cation provide similar benefits of self-assembly.
The six nickel CT complexes also have superior electrical properties to traditional organic CT complexes. Cation-anion interactions of inorganic based CT compounds, like the six nickel CT complexes described herein, are one of the key factors affecting their supramolecular packing and potential applications. Although purely organic charge-transfer salts exhibit interesting electronic and charge transport properties, the incorporation of metal centers into these materials leads to d-π interactions that enhance the electronic properties. Nickel CT complexes, for example, [Ni(dmit)2]−, (dmit=2-thioxo-1,3-dithiole-4,5-dithiolate), have previously been shown to form superconducting salts with both open- and closed-shell organic cations. A significant aspect of the solid-state interactions in this material is the overlap of the π-orbitals on the sulfur atoms with the metal d-orbitals that can enhance the electronic properties of the bulk material. Similarly, field-effect transistors fabricated with nickel bis(dithiolene) CT complexes have shown electron mobilities ranging from 3.0×10−6 to 2.8 cmV−1s−1. Some nickel bis(dithiolene) CT complexes were also found to exhibit comparable FET hole mobility and the transistors have been used to fabricate complementary circuits. Additionally, depending on the type of nickel donors and accepting counterparts, the assembly may be conductors or magnets. Crystals of conducting nickel CT compounds comprise highly ordered arrays of donor and acceptor species, one or both of which must be a radical ion that is thermodynamically stable. Besides the interaction between the orbitals on neighboring molecules, the electrical properties of CT complex are also strongly dependent on its band gap, i.e., if the band gap is large, the material would be insulating, while if the band gap becomes small, electrons transitions from the valence band to the conduction band can be very effective by the thermal excitation, leading to the intrinsic semiconductivity.
The six nickel CT complexes described herein take advantage of the benefits of self-assembly seen in organic-based CT complexes and the benefits of cation-anion interactions seen in inorganic-based CT complexes. Therefore, the six nickel CT complexes can be utilized to make highly efficient semiconducting devices (e.g., thin-film field-effect transistors or inverters) easily and inexpensively. Both the process for synthesizing the six nickel CT complexes and the process for fabricating semiconductor devices utilizing the six nickel CT complexes are easy and inexpensive. Accordingly semiconducting devices (e.g., thin-film transistors or inverters) utilizing one of the six nickel CT complexes can be utilized in electrical applications. One such electrical application is low frequency radio frequency identification (RFID) tag. The processes described herein can be applied on a large scale for commercial production of RFID tags by printing one of the six nickel CT complexes on flexible substrates.
The embodiments as disclosed and described in the application are intended to be illustrative and explanatory, and not limiting. Modifications and variations of the disclosed embodiments, for example, of the processes and apparatuses employed (or to be employed) as well as of the compositions and treatments used (or to be used), are possible; all such modifications and variations are intended to be within the scope of this application.

## Claims

1. A semiconductor device, comprising:
a substrate with a bilayer octadecylphosphonic acid (ODPA)/aluminum oxide (Al2O3) dielectric; and
a nickel charge transfer (CT) complex comprising a counter-cation of diquat or methyl-viologen applied on the substrate.

2. The semiconductor device of claim 1, wherein the nickel CT complex further comprises 2,3-pyrazinedithiol as a ligand.

3. The semiconductor device of claim 1, wherein the nickel CT complex further comprises 1,2-benzenedithol as a ligand.

4. The semiconductor device of claim 1, wherein the nickel CT complex further comprises 2,3-quinoxalinedithol as a ligand.

5. The semiconductor device of claim 1, wherein the nickel CT complex is uniformly deposited onto the substrate.

6. The semiconductor device of claim 1, applying the nickel CT complex is self-assembled on an active site of the substrate.

7. The semiconductor device of claim 6, further comprising:
a silver electrode situated on top of the substrate; and
a gold electrode situated on top of an active layer of the semiconductor device.

8. A semiconductor device, comprising:
a substrate comprising a bilayer of octadecylphosphonic acid (ODPA)/aluminum oxide (Al2O3) dielectric; and
a nickel charge transfer (CT) complex comprising a counter-cation of diquat or methyl-viologen on the substrate; and
a patterned source drain on the substrate.

9. The semiconductor device of claim 8, wherein the substrate is a flexible polyethylene terephthalate substrate.

10. The semiconductor device of claim 8, wherein the patterned source drain comprises a gold source drain contact.

11. The semiconductor device of claim 8, wherein the patterned source drain comprises a silver source drain contact.

12. The semiconductor device of claim 8, wherein the patterned source drain comprises a gate electrode on the substrate.

13. The semiconductor device of claim 8, wherein the nickel CT complex further comprises 1,2-benzenedithol as a ligand.

14. The semiconductor device of claim 8, wherein the nickel charge transfer complex is uniformly deposited onto the substrate.

15. A method, comprising:
fabricating a substrate with a bilayer octadecylphosphonic acid (ODPA)/aluminum oxide (Al2O3) dielectric; and
applying a nickel charge transfer (CT) complex comprising a counter-cation of diquat or methyl-viologen to the substrate.

16. The method of claim 15, wherein the fabricating the substrate further comprises fabricating the substrate with the bilayer ODPA/aluminum oxide (Al2O3) dielectric at room temperature.

17. The method of claim 15, wherein the applying the nickel CT complex further comprises applying the nickel CT complex comprising 2,3-pyrazinedithiol, 1,2-benzenedithol or 2,3-quinoxalinedithol as a ligand.

18. The method of claim 15, wherein the applying the nickel CT complex further comprises uniformly depositing the nickel CT complex onto the substrate.

19. The method of claim 15, wherein the applying the nickel CT complex further comprises self-assembling the nickel CT complex on an active site of the substrate.

20. The method of claim 15, further comprising incorporating the semiconductor device in a radio frequency identification tag.