1. Field of the Invention
The present invention relates to a tungsten oxide nanomaterial, and more particularly, to a sulfur-doped W18O49-type tungsten oxide nanomaterial and applications thereof.
2. Description of the Prior Art
Tungsten oxide (WOx) is a metal oxide with photoconductivity as well as a semiconductor. With the exciting of the photo energy, the valence electron can transit to the conduction band resulted in generating light current, and therefore can be applied as the light sensor. The tungsten oxide material is also characterized in gas absorption, and its resistance may change corresponding to gas absorption or desorption. Therefore, detecting the change of the resistance of the tungsten oxide material can be applied for gas detection.
The conventional WO3 is a canary yellow rhomboidal crystal in the room temperature, and has about 2.6 eV band gap. Light sensors or gas detectors made of tungsten oxide nanomaterial semiconductor material have increased surface-to-volume ratio in terms of enhanced surface activity, photoconductivity gain, detector sensitivity or improved reaction time of detecting gas. The tungsten oxide material reveals characteristics of semiconductor, and can be also applied as MOSFET (metal-oxide-semiconductor field-effect transistor) material. For example, WO3 Nanowires on Carbon Papers: Electronic Transport, Improved Ultraviolet-light Photo detectors and Excellent Field Emitters (Liang Li, Yong Zhang et al., on J. Mater. Chem., 2011, 21, 6525-6530), Ultraviolet Photoconductance of a Single Hexagonal WO3 Nanowire, by Kai Huang, Qing Zhang et al, published on Nano. Res. (2010) 3:281-287.
Since tungsten oxide nanomaterial can be applied to the detector, MOSFET and photoconductive devices, it's an important goal to increase the surface-to-volume ratio, and improve the sensitivity and photoconductivity gain so as to improve the photovoltaic efficiency.
In one embodiment of the present invention, a sulfur-doped W18O49-type tungsten oxide nanomaterial is represented by a chemical formula (I): W18O(49-x)Sx . . . (I), wherein x ranges from 0.5 to 5.5. The W18O49-type tungsten oxide nanomaterial of the present invention utilizes a precursor containing WS2, and fabricated by a deposition process after a thermal oxidation reaction.
In another embodiment of the present invention, a light sensor comprises a substrate, an electrode unit, a photoelectric conversion unit, and a current detecting unit. The electrode unit is configured on the substrate and has a first electrode and a second electrode. The photoelectric conversion unit is configured on the substrate, electrically connected to the first electrode and the second electrode. The photoelectric conversion unit comprises the sulfur-doped W18O49-type tungsten oxide nanomaterial. The photoelectric conversion unit is illuminated by a light to generate light current. The current detecting unit is electrically connected to the first electrode and the second electrode and configured for detecting the light current passing through the first electrode and the second electrode.
In yet another embodiment of the present invention, a metal-oxide-semiconductor field-effect transistor comprises a substrate, an oxide layer, a source/drain electrode, a semiconductor channel layer, and a gate electrode. The oxide layer is formed on the substrate, and the source/drain electrode is formed on the oxide layer. The semiconductor channel layer is configured on the oxide layer and a channel is formed between the source/drain electrodes. The channel comprises the sulfur-doped W18O49-type tungsten oxide nanomaterial. The gate electrode is configured on the lower surface of the substrate.
In still another embodiment of the present invention, a solar cell comprises a first substrate, a second substrate, a light absorption layer, and an n-type semiconductor layer. The first substrate has a first electrode, and the second substrate has a second electrode. The light absorption layer is located between the first substrate and the second substrate, wherein the light absorption layer comprises the sulfur-doped W18O49-type tungsten oxide nanomaterial. The n-type semiconductor layer is located between the light absorption layer and the second substrate.
The sulfur-doped W18O49-type tungsten oxide nanomaterial of the present invention is a new semiconductor material that dopes the sulfur to increase the light absorption rate and spectrum. The light absorbing wavelength is between 300-1400 nm, and the light absorption efficiency is about 80%. The band gap is modulated and reduced to 1.7 eV by doping the sulfur, and the lower band gap may improve the photoconductivity gain. The W18O49-type tungsten oxide material has the characteristics of photoconductivity as well as gas absorption so as to be applied in light/gas detectors, MOSFET and solar cell to improve the sensitivity and power conversion efficiency.
Other advantages of the present invention will become apparent from the following descriptions taken in conjunction with the accompanying drawings wherein certain embodiments of the present invention are set forth by way of illustration and examples.
The foregoing aspects and many of the accompanying advantages of this invention will become more readily appreciated as the same becomes better understood by reference to the following detailed descriptions, when taken in conjunction with the accompanying drawings, wherein:
a is a schematic diagram showing the process flow for fabricating the W18O(49-x)Sx nanomaterial according to one embodiment of the present invention;
b is a schematic diagram showing the W18O(49-x)Sx nanomaterial formed on the substrate according to one embodiment of the present invention;
c is an X-ray diffraction pattern of the W18O(49-x)Sx nanomaterial of the present invention;
d is an absorption spectrum of the W18O(49-x)Sx nanowire of the present invention;
a is a scanning electron microscope (SEM) image showing the W18O(49-x)Sx nanostructure of the present invention, using a precursor containing 100% WS2;
b is a scanning electron microscope (SEM) image showing the W18O(49-x)Sx nanostructure of the present invention, using a precursor containing 66.7% WS2;
c is a scanning electron microscope (SEM) image showing the W18O(49-x)Sx nanostructure of the present invention, using a precursor containing 40% WS2;
d is a scanning electron microscope (SEM) image showing the W18O(49-x)Sx nanostructure of the present invention, using a precursor containing 10% WS2;
a is a diagram showing (αhv)2-band gap value of the W18O45.96S3.04 nanowire of the present invention;
b is a diagram showing (αhv)2-band gap value of the W18O47.63S1.37 nanowire of the present invention;
a is a schematic diagram showing a light sensor according to one embodiment of the present invention;
b is a diagram showing the relation of light intensity and light current when illuminating the photoelectric conversion unit in the light sensor according to one embodiment of the present invention;
a is a schematic diagram showing a MOSFET according to one embodiment of the present invention;
b is a diagram showing the relation of Ids-Vg measured in the MOSFET according to one embodiment of the present invention; and
The present invention is directed to providing a sulfur-doped W18O49-type tungsten oxide nanomaterial having the chemical formula (I):
W18O(49-x)Sx . . . (I), wherein x ranges from 0.5 to 5.5, and x ranges from 2 to 4, preferably.
The sulfur-doped W18O49-type tungsten oxide (hereinafter abbreviated as W18O(49-x)Sx) nanomaterial of the present invention utilizes a precursor comprising WS2, and is fabricated by a deposition process after a thermal oxidation reaction. As shown in
The precursor may also comprise other reductants such as SnCl2, and the doped ratio of sulfur in the W18O49-type tungsten oxide nanomaterial may be adjusted with the SnCl2/WS2 ratio in the precursor. During the process, WS2 is oxidized to WO3, and partial WO3 is reduced to WO2 by Sn2+ from SnCl2, wherein W18O49 composed of WO2 and WO3 is formed on the substrate 10 and prevents from over-oxidization. When operated in the same process conditions (temperature, pressure and O2 flow rate), the higher ratio of WS2 in the precursor (in terms of lower SnCl2), the more sulfur doped in the W18O49-type tungsten oxide. The X in the W18O(49-x)Sx may reach 5.5 for the highest value. In a preferred embodiment, the WS2 ratio in the precursor is 20-80% and the x of the fabricated W18O(49-x)Sx may range from 2 to 4. Besides, factors such as the temperature, pressure and O2 flow rate may also be operated to adjust the doped ratio of sulfur.
In the above-mentioned process, the precursor is mainly composed of SnCl2 and WS2. Here, it is known that the sulfur is a VI element and accordingly, the precursor may also contain other the chemical compounds having other VI elements (such as Se or Te), such as WSe2 or WTe2. In the above-mentioned process, partial O in W18O49 may be replaced by Se or Te in the precursor comprising WSe2 or WTe2 in the thermal oxidation reaction so as to fabricate W18O(49-x)Sx nanomaterials doped with Se or Te, in addition to sulfur.
The sulfur-doped W18O49 fabricated in the present invention is blue in color and the chemical formula is W18O49-xSx. The doped ratio of sulfur in W18O(49-x)Sx may be determined by process parameters such as chamber temperature (high temperature area), the substrate temperature (low temperature area), ratio of the precursor (SnCl2 and WS2), and gas flow rate (O2 and Ar). For example, when the substrate temperature is raised to 500, the W18O49-xSx formed on the substrate is determined to be W18O45.96S3.04 based on quantitative chemical composition analysis. When the substrate temperature is raised to 600° C., the W18O49-xSx formed on the substrate is W18O47.63S1.37.
Among the process parameters mentioned above, the structure and morphology of the W18O49-type tungsten oxide may be affected by the ratio of WS2 in the precursor and the substrate temperature, and the different types of nanomaterials such as nanowire, nanorod, nanotube or thin film structure may be formed specifically by adopting different parameters such as composition ratio of the precursor and substrate temperature.
The first embodiment of the present invention utilizes the chemical vapor deposition (CVD) process to fabricate the sulfur-doped W18O49-type tungsten oxide nanomaterial. As shown in
c is an X-ray diffraction pattern of the W18O(49-x)Sx nanomaterial fabricated according to the first embodiment of the present invention. The diffraction peak in the
The effects of different factors, such as weight ratio of WS2 and SnCl2 in the precursor to W18O49-xSx nanomaterial structure are now described. With other process variables fixed, namely substrate temperature=500° C., chamber temperature=700-900° C., and ratio of O2 and Ar=0.2%, the single variable, the ratio of WS2 in the precursor, was changed and the W18O49-xSx with different structures was then obtained. Refer to
The optical characteristics of the W18O49-xSx nanomaterial of the present invention are now described. Regarding light absorption, the measurement method is using a blank glass slide for baseline correction first to prevent the effect of glass slide in reflection and absorption spectrum. The measured transmission of the slide is Abs %=100−Trans %−Ref %, where Abs is the absorption efficiency of the present material, Trans is the transmission of the glass slide, and Ref is the reflection. As shown in
In
Please refer to
The W18O45.96S3.04 nanowire of the present invention is characterized in full spectrum light absorption according to the above analysis and in the second embodiment, the light sensor utilizes the photoelectric conversion unit 14 with W18O45.96S3.04 nanowire. The illuminating light is 532 nm green light, and has about 20W/m2 intensity.
wherein Iph is the light current, q is the elementary charge, P is the light intensity, h is the Plank constant, and v is the light frequency. After calculation, the light sensor using the W18O45.96S3.04 nanomaterial as the photoelectric conversion unit 14 has a photoconductivity gain about 107.
The photoelectric conversion unit 14 comprising W18O49-xSx nanomaterial of the light sensor in the second embodiment 1 also has the characteristic of gas absorption; therefore, the light sensor in the second embodiment may also be used as a gas detector. Here, the resistance value of the photoelectric conversion unit 14 changes after absorbing gas and may be used for detecting gas. In the case of detecting NO2, the photoelectric conversion unit 14 comprising the W18O49-xSx nanomaterial is an n-type semiconductor. After absorbing NO2, an oxidative gas with electron affinity higher than O2, the space charge of the sulfur-doped tungsten oxide may be increased with electrons captured NO2 and the resistance of the photoelectric conversion unit 14 is thus increased. The current detecting unit 16 may be used for monitoring the light current passing through the first electrode 12a and the second electrode 12b to determine whether the gas has been detected by the photoelectric conversion unit 14.
In the third embodiment of the present invention, a metal-oxide-semiconductor field-effect transistor comprises a substrate 10, an oxide layer 11, a source electrode S, a drain electrode D, and a semiconductor channel layer 13. The oxide layer 11 is an insulation layer formed on the substrate 10, and the source electrode S and the drain electrode D are formed on the oxide layer 11. The semiconductor channel layer 13 is configured on the oxide layer 11 to form a channel between the source electrode S and the drain electrode D, and a gate electrode G is configured on the lower surface of the substrate 10.
Please refer to
In the fourth embodiment of the present invention, a solar cell comprises a first substrate 21, a second substrate 22, a light absorption layer 23, and a semiconductor layer 24. A first electrode 211 is configured on the first substrate 21. The light absorption layer 23 comprises W18O49-xSx nanomaterial. The semiconductor layer 24 is configured on the light absorption layer 23. Then, a second electrode 222 is configured on the second substrate 22.
Please refer to
The sulfur-doped W18O49-xSx nanomaterial tungsten oxide with nanowire structure in has a minimum external diameter about 10 nm, a high surface-to-volume ratio, a wide light absorption spectrum, a wave length in the range of 300-1400 nm, a light absorption rate about 80% (95% maximum). In the case of W18O45.96S3.04 nanowire, it may reach 7.8×104 cm−1 absorption coefficient, and a low band gap 1.7 eV by doping sulfur. The sulfur-doped nanomaterial tungsten oxide of the present invention is provided with great photovoltaic transforming efficiency. Therefore, photoconductivity gain of the fabricated light sensor may reach 107 and is much higher than that (G=4.6×103) in conventional WO3 nanomaterial. With the above characteristics, the sulfur-doped nanomaterial tungsten oxide of the present invention may be applied in light/gas detector and solar cell and highly improve the sensor sensitivity and the photovoltaic transforming efficiency of the solar cell.
While the invention can be subject to various modifications and alternative forms, a specific example thereof has been shown in the drawings and is herein described in detail. It should be understood, however, that the invention is not to be limited to the particular form disclosed, but on the contrary, the invention is to cover all modifications, equivalents, and alternatives falling within the spirit and scope of the appended claims.
Number | Date | Country | Kind |
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102133608 | Sep 2013 | TW | national |