TWI395336B - Optoelectronic semiconductors, conductors, insulators and their design methods with multiple high entropy alloy oxides - Google Patents

Description

Photoelectric semiconductor, conductor, insulator and design method thereof with multi-element high-entropy alloy oxide

The invention relates to an alloy oxide, in particular to an optoelectronic semiconductor, a conductor, an insulator oxidized by a multi-element high-entropy alloy, and a design method thereof.

Multr-element High-Entropy Alloys are alloys that replace the traditional use of a single principal component with a multi-component main component, that is, an alloy composed of a variety of major elements, each of which has a high but high Not more than 35 at% of the atomic percentage, therefore, no major element occupies 50 at% and becomes the only major element.

It has been found from previous studies that multi-enriched high-entropy alloys promote uniform mixing of major elements due to high entropy effect, so it is easy to form body-centered cubic (BCC), face-centered cubic (FCC) crystals, or Structures such as amorphous, and in terms of material properties, exhibit high hardness, high temperature softening resistance, high temperature oxidation resistance, corrosion resistance, etc. In addition, the microstructure of multi-element high-entropy alloys is diffused and redistributed due to multiple elements. The tendency to nanocrystallization, for the rapid solidification or vacuum coating process, shows a tendency to amorphization, so it has great industrial potential in material applications.

On the other hand, Transparent Conducting Oxide (TCO) is one of the key materials for photovoltaic components. The main applications are, for example, flat panel displays (FPD), solar cells, touch panel screens, A transparent electrode of a photovoltaic element such as an e-book can be generally classified into an n-type transparent conductive oxide such as ITO, ZnO, and SnO ₂ , and, for example, CuAlO ₂ , CuCrO ₂ , CuFeO _{2 ,} and SrCu ₂ O ₂ . Two types of p-type transparent conductive oxides.

However, the existing n-type transparent conductive oxide, such as ZnO, is a wurzite hexagonal structure, and a p-type transparent conductive oxide such as CuAlO ₂ , CuCrO ₂ , and CuFeO ₂ is a black copper iron ore structure (Delafossite structure) According to the literature, the black copper iron ore structure is anisotropic and less prone to synthesis at room temperature.

Therefore, if the diversity and superior properties of high-entropy alloys can be applied, the development of materials suitable for the field of optoelectronic technology will enable optoelectronic technology to take a big step forward.

Since there is no research on the development of optoelectronic materials with high-entropy alloys, and high-entropy alloys are the main elements because of the composition of the elements, the alloy systems that can be developed are countless, so On the premise of no development basis, the inventor's research team selected zinc (Zn) and tin from the existing transparent conductive oxides such as ITO, ZnO, SnO ₂ , CuAlO ₂ , CuCrO ₂ and TiO ₂ :Nb. (Sn), copper (Cu), titanium (Ti), and niobium (Nb) are high-entropy alloys as main elements, and are combined with oxygen to form high-entropy alloy oxides.

The result is surprising. When the atomic percentage of controlling oxygen is in the range of 40at% to 80at% of the ceramic material and increases from 40at%, the multi-element high-entropy alloy and oxygen are regularly combined into a conductor and a photoelectric Characteristics of semiconductors and transparent insulators.

Accordingly, the present invention provides a method for designing a ceramic material having a multi-element high-entropy alloy, which is selected from the group consisting of zinc, tin, copper, titanium, and tantalum to form a multi-element high-entropy alloy, wherein zinc, tin, copper, titanium, and niobium The atomic percentage accounts for 3.00at%~13.00at% of the multi-element high-entropy alloy, respectively, and the oxygen is adjusted to account for 51.00at%~57.00at% of the multi-high-entropy alloy, so that the multi-element high-entropy alloy and oxygen combine to form an optoelectronic semiconductor.

In addition, by adjusting the atomic percentage of oxygen to not more than 50.5 at%, the multi-element high-entropy alloy can be combined with oxygen to form a conductor; if the atomic percentage of oxygen is adjusted to be greater than 59.00 at%, the multi-element high-entropy alloy is combined with oxygen to form a transparent insulator.

The utility model has the advantages of providing a novel photoelectric semiconductor, a conductor and a transparent insulator composed of a plurality of high-entropy alloys composed of zinc, tin, copper, titanium and bismuth and oxygen, in addition to enriching the current alloy oxide In addition to the system, it is also possible to promote the technological development of photovoltaic elements for the application of photovoltaic elements.

The above and other technical contents, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments.

The inventors used a Zn _0.2 Sn _0.2 Cu _0.2 Ti _0.2 Nb _0.2 target with a base pressure of 3.0 × 10 ^-6 Torr, a working pressure of 3.0 × 10 ^-3 Torr, and an RF power of 200 W. And the oxygen/oxygen + argon atmosphere ratio (O ₂ /O ₂ +Ar ratio) is 4.4%, 4.7%, 5.0%, 5.3%, and the target-substrate spacing is 70mm. Sputtering for 20 minutes, respectively, on a glass substrate (Zn _8.2 Sn _10.3 Cu _11.3 Ti _8.7 Nb _11.2 ) _49.7 O _50.3 (hereinafter referred to as the first alloy oxide), (Zn _12.8 Sn _5.4 Cu _12.1 Ti _7.9 Nb _10.1 ) _48.4 O _51.6 (hereinafter referred to as the second alloy oxide) (Zn _11.7 Sn _7.3 Cu _8.5 Ti _7.1 Nb _9.4 ) _44.0 O _56.0 (hereinafter referred to as the third alloy oxide) (Zn _12.23 Sn _10.2 Cu _9.1 Ti _3.5 Nb _5.6 ) _40.8 O _59.2 (hereinafter referred to as the fourth alloy oxide).

Referring to Fig. 1, Fig. 1 is an X-ray diffraction pattern of first, second, third and fourth alloy oxides. It can be seen from the results of the figures that the first, second, third and fourth alloy oxides are all amorphous structures.

Referring to Figures 2, 3, 4, and 5, Figures 2, 3, 4, and 5 are the ordinates of the intensity (au) of zinc, copper, titanium, and tantalum, respectively. eV)) X-ray photoelectron spectroscopy of the first, second, third and fourth alloy oxides obtained from the abscissa, and the four graphs can verify the oxidation of the first, second, third and fourth alloys. As the percentage of oxygen atoms increases, the binding energy of the first, second, third, and fourth alloy oxides increases, that is, the valence electrons are removed or the oxidation state increases, that is, the multi-element high-energy alloy oxides are oxygen-dependent. The atomic percentage increases while the optical energy gap increases, and the conductivity decreases. In other words, the present invention does adjust the percentage of oxygen atoms in a predetermined range of oxygen atomic percentages to form conductors, semiconductors, and insulators.

Referring to FIG. 6, FIG. 6 is a graph showing the transmittance of the first, second, third, and fourth alloy oxides to the full-wavelength light at thicknesses of 364 nm, 292 nm, 277 nm, and 209 nm, respectively, and the measurement results are known to be conservative. When the film thickness of the second, third and fourth alloy oxides is not more than 300 nm, the visible light has a certain degree of transmittance, and the thinner the film thickness, the higher the transmittance, but the main cause is the high-entropy alloy oxide. The optical energy gap increases as the percentage of oxygen atoms increases, that is, the second and third alloy oxides are not semiconductors, but are optoelectronic semiconductors having a certain degree of transmittance for visible light.

Referring to FIG. 7, FIG. 8 and FIG. 9, FIG. 7, FIG. 8, and FIG. 9 are respectively the indirect energy gaps of the second, third, and fourth alloy oxides, and the first alloy oxide is The opaque conductor does not have an energy gap. It can be indirectly verified from Fig. 7, Fig. 8 and Fig. 9 that the indirect energy gap increases from 1.69eV to 2.66eV, and the second and third alloys are gradually increased. The oxide is a semiconductor and the fourth alloy oxide is an insulator.

Further, the material properties of the first, second, third, and fourth alloy oxides are organized as follows, and the present invention can be further verified.

In summary, the present invention mainly provides a novel design method for combining a multi-element high-entropy alloy and oxygen into an optoelectronic semiconductor, a conductor, a transparent insulator, and the like, and the atomic percentage of oxygen can be 40 at%. In the range of 80at%, the composition of the precise oxygen and the multi-entropy alloy is obtained as a transparent insulator, an optoelectronic semiconductor, and a photoelectric material such as a conductor, in addition to a system that can enrich the current alloy oxide, and can also be used for optoelectronics. The application of components to promote the technical development of photovoltaic elements has indeed achieved the object of the present invention.

The above is only the preferred embodiment of the present invention, and the scope of the invention is not limited thereto, that is, the simple equivalent changes and modifications made by the scope of the invention and the description of the invention are All remain within the scope of the invention patent.

1 is an X-ray diffraction diagram illustrating the verification of the four alloy oxide produced by the experiment of the present invention as an amorphous structure;

2 is a photoelectric spectrum diagram illustrating the relationship between the absorption intensity of zinc photoelectron and the binding energy in the four-alloy oxide produced by the experiment of the present invention;

3 is a photoelectric spectrum diagram illustrating the relationship between the absorption intensity of copper photoelectron and the binding energy in the four-alloy oxide produced by the experiment of the present invention;

Figure 4 is a photoelectric spectrum diagram illustrating the relationship between the absorption intensity of titanium photoelectron and the binding energy in the four-alloy oxide produced by the experiment of the present invention;

Figure 5 is a photoelectric spectrum diagram illustrating the relationship between the absorption intensity of the photoelectron and the binding energy in the four-alloy oxide produced by the experiment of the present invention;

Figure 6 is a graph of light transmittance, illustrating the light transmittance of a four-alloy oxide produced by the experiment of the present invention for a wavelength of 200-1000 nm;

Figure 7 is an indirect energy gap diagram illustrating the indirect energy gap of a second alloy oxide produced by the experiment of the present invention;

Figure 8 is a non-direct energy gap diagram illustrating the indirect energy gap of a third alloy oxide produced by the experiment of the present invention;

Figure 9 is a non-direct energy gap diagram illustrating the indirect energy gap of a fourth alloy oxide produced by the experiment of the present invention.

Claims (6)

A method for designing an optoelectronic semiconductor having a multi-element high-entropy alloy oxide, comprising: (a) selecting zinc, tin, copper, titanium, and tantalum to form a multi-element high-entropy alloy, wherein zinc, tin, copper, titanium, and niobium account for The atomic percentage of the multi-element high-entropy alloy is 3.00at% to 13.00at%; and (b) the oxygen percentage of the optoelectronic semiconductor is adjusted to be 51.00at% to 57.00at%, and the multi-element high-entropy alloy is combined with oxygen to form a photoelectric semiconductor. The method for designing an optoelectronic semiconductor having a multi-element high-entropy alloy oxide according to claim 1, wherein the step (b) re-adjusts the atomic percentage of oxygen to not more than 50.5 at% to make the multi-element high-entropy alloy and oxygen Combined into a conductor. The method for designing an optoelectronic semiconductor having a multi-element high-entropy alloy oxide according to claim 1, wherein the step (b) further adjusts the atomic percentage of oxygen to be greater than 59.00 at% to make the multi-element high-entropy alloy and oxygen Combined into a transparent insulator. An optoelectronic semiconductor of a multi-element high-entropy alloy oxide, comprising: an atomic percentage of 51.00 at% to 57.00 at% of oxygen, and a multi-element high-entropy alloy occupying a remaining atomic percentage component, and the multi-element high-entropy alloy is zinc, tin, Copper, titanium, and niobium are formed, wherein zinc, tin, copper, titanium, and niobium respectively account for 3.10at% to 13.00at% of the total atomic percentage of the optoelectronic semiconductor. A multi-element high-entropy alloy oxide conductor comprising: oxygen having an atomic percentage of not more than 50.50 at%, and a multi-element high-entropy alloy accounting for a percentage of residual atoms, and the multi-element high-entropy alloy is zinc, tin, copper, titanium, and tantalum The composition, wherein zinc, tin, copper, titanium, and yttrium respectively account for 3.10 at% to 13.00 at% of the total atomic percentage of the conductor of the multi-element high-entropy alloy oxide. A transparent insulator of a multi-element high-entropy alloy oxide comprising: oxygen having an atomic percentage greater than 59.00 at% and not exceeding 80.00 at%, and a multi-element high-entropy alloy occupying a percentage of residual atoms, and the multi-element high-entropy alloy is zinc, tin, Copper, titanium, and niobium, wherein zinc, tin, copper, titanium, and niobium respectively account for 3.10at% to 13.00at% of the total atomic percentage of the conductor of the multi-element high-entropy alloy oxide.