Patent Application
20180158971
This application claims priority from Korean Patent Application No. 10-2016-0164143 filed on Dec. 05, 2016 in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference in its entirety.
The present invention relates to a transparent photoelectric element and a method for fabricating the same. More specifically, the present invention relates to a transparent photoelectric element having high transparency and high conversion efficiency and a method for fabricating the same.
Global warming is a fatal problem for human beings living on Earth. Past energy production has been mainly accompanied by the generation of greenhouse gas, in which a composition ratio of the Earth's atmosphere has significantly increased, and such greenhouse gas has caused a sea level rise and the destruction of ozone responsible for filtering of ultraviolet rays. Due to the increase in the greenhouse gases, human beings are experiencing the shortage of the area of the living earth and the shortage of breath oxygen. Furthermore, excessive ultraviolet radiation comes into direct-contact with the human body, which causes severe risks such as skin discoloration, immune function deterioration, photo-aging and skin cancer.
Energy production using solar cells is one of the ultimate forms of electricity generation performed without the production of greenhouse gases. However, since conventional general solar cells include dark semiconductor films (or wafers), they have clear transparency limitation in direct application to the on-site energy generation of buildings or vehicles.
An aspect of the present invention provides a transparent photoelectric element with improved operating performance.
Another aspect of the present invention provides a method for fabricating a transparent photoelectric element with improved operating performance.
The aspects to be solved by the present invention are not limited to the aspects mentioned above and another aspect which is not mentioned can be clearly understood by those skilled in the art from the description below.
According to an aspect of the present inventive concept, there is provided a method for fabricating a transparent photoelectric element, the method comprising providing a transparent substrate, forming a transparent conductive film on the transparent substrate at room temperature, forming an n-type oxide semiconductor film on the transparent conductive film and forming a p-type nickel oxide film having a quantum dot structure on the n-type oxide semiconductor film through reactive sputtering at room temperature, the reactive sputtering including oxygen and argon, a ratio of oxygen being smaller than a ratio of argon.
According to another aspect of the present inventive concept, there is provided a transparent photoelectric element comprises a transparent flexible PET (polyethylene terephthalate) substrate, a transparent conductive film formed on the transparent flexible PET substrate, the transparent conductor including ITO (Indium Tin Oxide) or FTO (fluorine-doped tin oxide), an n-type oxide semiconductor film formed on the transparent conductive film and a p-type nickel oxide film formed on the n-type oxide semiconductor film and forming a heterojunction with the n-type oxide semiconductor film, wherein exciton occurs in the heterojunction, and the p-nickel oxide film has a quantum dot structure.
According to still another aspect of the present inventive concept, there is provided a transparent photoelectric element comprising a first laminated structure which includes a first glass substrate, a first transparent conductor film formed on the first glass substrate, a first FTO film formed on the first transparent conductor film, and a first NiO film formed on the first FTO film and forming a heterojunction with the first FTO film, a second laminated structure which includes a second glass substrate, a second transparent conductor film formed on the second glass substrate, a second FTO film formed on the second transparent conductor film, and a second NiO film formed on the second FTO film and forming a heterojunction with the second FTO film and a bonding wire which connects the first and second laminated structures
According to an embodiment of the present invention, at least the following effects are obtained.
That is, the transparent photoelectric element according to some embodiments of the present invention is wholly completely transparent, flexible and cuttable.
Also, the transparent photoelectric element according to some embodiments of the present invention can have a high open voltage and a very fast reaction rate.
Furthermore, the transparent photoelectric element according to some embodiments of the present invention can have the highest efficiency of the transparent solar cell.
The effects of the present invention are not limited by the contents exemplified above, and various effects are further included in this specification.
The patent or application file contains at least one drawing executed in color. Copies of this patent or patent application publication with color drawing(s) will be provided by the Office upon request and payment of the necessary fee.
The above and other aspects and features of the present invention will become more apparent by describing in detail exemplary embodiments thereof with reference to the attached drawings, in which:
Hereinafter, a method for fabricating a transparent photoelectric element according to some embodiments of the present invention will be described with reference to
Referring to
The transparent substrate 100 may be, for example, a flexible substrate. That is, the transparent substrate 100 may have characteristics that are freely bent and then restored. In this case, the transparent substrate 100 may be a plastic substrate. At this time, the transparent substrate 100 may be, for example, a PET (polyethylene terephthalate) substrate.
The transparent substrate 100 may not be a flexible substrate. The transparent substrate 100 may also be a transparent glass substrate. The material of the transparent substrate 100 may vary depending on the performance and purpose of the device.
The transparent substrate 100 may be a substrate without any color.
Subsequently, a transparent conductive film 200 is formed on the transparent substrate 100.
The transparent conductive film 200 may include ITO or FTO. The transparent conductive film 200 may be formed by sputtering at room temperature.
Subsequently, referring to
The n-type oxide semiconductor film 300 may include at least one of ZnO, AZO, TiO and SnS. The n-type oxide semiconductor film 300 may also be a transparent film material. The n-type oxide semiconductor film 300 may be formed by RF sputtering. The process of forming the n-type oxide semiconductor film 300 may also be performed at room temperature.
Subsequently, referring to
The p-type nickel oxide film 400 may be formed by a reactive sputtering method. Specifically, the p-type nickel oxide film 400 may be formed, using a pure nickel or NiO target, and using argon (Ar) and oxygen (O2). At this time, the ratios of argon and oxygen may be different from each other. That is, the ratio of argon may be higher than the ratio of oxygen. At this time, oxygen may have a ratio of 1 to 20% compared with argon.
When the oxygen exceeds 20% compared with argon, it may be difficult to form a quantum dot of a nickel oxide film, that is, a quantum dot structure. When the oxygen is less than 1% compared with argon, the oxide film components of the nickel oxide film may not be properly formed.
The quantum dot, that is, the quantum dot structure described above may perform the function of a protective film (surface passivation) on the surface of the zinc oxide film being in contact with the nickel oxide film. Thus, an exciton or exiton phenomenon which has not occurred in the past may occur.
All of the transparent conductive film 200, the n-type oxide semiconductor film 300 and the p-type nickel oxide film 400 may be deposited in-situ. That is, the transparent conductive film 200, the n-type oxide semiconductor film 300, and the p-type nickel oxide film 400 may be continuously formed in the same sputtering chamber.
The transparent photoelectric element formed by the method of
A PET flexible substrate was used for the transparent substrate 100. The PET flexible substrate has no color and has a thickness of 100 μm. The PET flexible substrate was cleaned by ultrasonication of distilled water.
The transparent conductive film 200 was deposited as the ITO film. The ITO film may perform a sputtering process of an ITO target (10 wt. % SnO2 containing In2O2) on the PET flexible substrate with an output density of 3.7 W/cm2. During the ITO sputtering, argon and oxygen may be supplied at 30 sccm and 0.3 sccm, respectively. The ITO film was deposited with a thickness of 300 nm.
The n-type oxide semiconductor film 300 was deposited as a ZnO film. The ZnO film may be deposited by the RF sputtering system. At this time, the RF power may be 3.58 W/cm2. The ZnO target can have a purity of 99.99%. The ZnO film was deposited to a thickness of 100 nm.
Finally, the p-type nickel oxide film 400 was formed by reactively sputtering a Ni target with purity of 99.999% at the output of 3.70 W/cm2 in the presence of argon and oxygen gas. At this time, argon and oxygen gases are supplied at 30 sccm and 1 sccm, respectively. The operating pressure valve may be maintained at 5 mTorr. The base pressure before the operating pressure may be maintained at 5×10−5 Torr. The nickel oxide film was deposited with a thickness of 30 nm.
A nickel oxide film was directly deposited on the PET flexible substrate with a thickness of 30 nm by reactive sputtering.
In order to investigate the characteristics of the interface of first example and first comparative example, the FESEM and HRTEM photographs of the respective interfaces were analyzed.
Referring to
Since the NiO film has the quantum dot structure, the energy level (or state) of the NiO film may have a discrete density divided into several sections. The energy levels with discrete density may very rapidly promote the transfer of holes separated from the exciton by incident light. Therefore, the photoresponse rate of the transparent photoelectric element of the first example of the present invention as a photodetector can be greatly improved.
Furthermore, since the NiO film has the quantum dot structure, the surface energy state of the interface between the NiO film and the ZnO film may be reduced. That is, the quantum dot structure of the NiO film may act as a passivation film on the surface of the ZnO film. As a result, the interface characteristics of the heterojunction of the NiO film and the ZnO film formed at room temperature can be greatly improved.
In order to examine the optical characteristics, the transmittance (T), the reflection (R) and the absorbance (A) of the transparent photoelectric element of the first example were examined.
Referring to
On the other hand, in order to investigate
Referring to
TEM (transmission electron microscopy) and EDS (energy-dispersive X-ray spectroscopy) were analyzed to check the interface characteristics of the transparent photoelectric element of the first example.
Referring to
In order to investigate the characteristics as an ultraviolet photodetector, the transparent photoelectric element of the first example was mounted on an ultraviolet ray source (365 nm wavelength, 3 mW/cm2).
Referring to
The probe 500 includes a first probe 510 and a second probe 520 corresponding to the anode and the cathode, respectively. At this time, the first probe 510 may be brought into contact with the ITO film, and the second probe 520 may be brought into contact with the NiO film.
At this time, the transparent photoelectric element of the first example does not include any opaque electrode, and the probe 500 may include tungsten coated with Au, but is not limited thereto.
Referring to
In order to evaluate the transparent photoelectric element of the first example as a self-bias photodetector, the intensity of ultraviolet ray was changed from 10 μW/cm2 to 3 mW/cm2.
The photoresponse ratio PR, which is an important factor in the photodetector, is a ratio of a light-on current ION and a light-off current IOFF. That is, the photoresponse ratio is defined as PR=ION/IOFF.
Referring to
Furthermore, the self-biased photodetector according to the first example is very sensitive and may detect extremely small ultraviolet ray such as 10 μW/cm2.
In order to evaluate the instantaneous photoresponse of the transparent photoelectric element of the first example, the photoresponse time was detected.
Referring to
Various voltages were applied to the transparent photoelectric element of the first example in order to evaluate the bias-responses of the transparent photoelectric element of the first example.
Referring to
The rapid photoresponse may be attributed to the regulatory effect of the space charge region. When an electric field is applied to the exciton, the separated charges and holes move in opposite directions. According to the Bore model, the free exciton's energy is the same as 2 Rx/(qax) in the ground state. Here, Rx is the rydberg energy of the exciton, q is the charge of the electrons, and ax is a bore radius of the polycrystalline ZnO. If the electric field exceeds the value of free exciton, exciton may be separated by field ionization.
In the transparent photoelectric element of the first example of the present invention, as the applied bias is adjusted, it is possible to acquire a much faster photoresponse by efficient formation of generation of free excitons and efficient separation according to field ionization.
An important evaluation factor of a photodetector is response R* and detection D*. The responsen is defined by R*=Iph/Pin where Iph and Pin mean the photocurrent and the light intensity, respectively. The detection is defined by D*=R*/(2qJd)1/2 where Jd means the background current density.
Three types of bias conditions (zero bias in the self-operating mode, forward bias in the field ionization mode, and reverse bias in the photoconductive mode) may be given to the photodetector using the transparent photoelectric element of the first example.
Under the zero bias condition, response and detection are exhibited as 20 μA/W and 7.2×1011 Jones, respectively. Performance of enhanced response (1 mA/W) and detection (4.58×1012 Jones) is obtained in the photoconductive mode. However, the photoresponse (τr=370 μs and τf=840 μs) may be delayed by its own intrinsic operation mode, unlike the rapid photoresponse of the field ionization mode. That is, the photodetector of the transparent photoelectric element of the first example of the present invention may have excellent photodetection characteristics and enhanced performance intentionally selected in a special mode.
In order to evaluate the characteristics of the transparent photoelectric element of the first example as a solar cell, the voltage-current characteristics under the dark condition and the illumination condition were measured.
Referring to
At the incidence of ultraviolet ray (λ=365 nm, 3 mW/cm2), the transparent photoelectric element of the first example apparently provides photovoltaic characteristics of a very large open circuit voltage (Voc) of 1.33 V, a short circuit current density (Jsc) of 27.2 μA/cm2, and a fill factor (FF) of 77.3%.
The photoelectric element according to the first example of the present invention is a photodetector and a solar cell, which has an ultrafast photoresponse, does not need a metal contact, is totally transparent, is flexibly bent and then restored, and is very light. Therefore, through these advantages, the photoelectric element may be variously applied in the field of solar cells. For example, the photoelectric element of the first example of the present invention may be used as a transparent film integrated in a window of a building or a vehicle. Such a transparent film can achieve the ultimate goal of energy management to generate on-site power.
As the transparent substrate, a glass substrate was used. A transparent conductive film 200 was deposited as the FTO film. The FTO film was coated on the glass substrate. The n-type oxide semiconductor film 300 was deposited as a ZnO film, and a p-type nickel oxide film 400 was deposited thereon. In other words, the NiO/ZnO/FTO/glass structure was finally formed.
Referring to
At this time, the transparent photoelectric element before separation may have, but is not limited to, a size of 3 mm×3 mm.
Referring to
The first transparent photoelectric element unit 10 may include a first transparent substrate 100, a first transparent conductive film 200, a first n-type oxide semiconductor film 300, and a first p-type nickel oxide film 400. The second transparent photoelectric element unit 11 may include a second transparent substrate 101, a second transparent conductor film 201, a second n-type oxide semiconductor film 301, and a second p-type nickel oxide film 401. The third transparent photoelectric element unit 12 may include a third transparent substrate 102, a third transparent conductor film 202, a third n-type oxide semiconductor film 302, and a third p-type nickel oxide film 402. The fourth transparent photoelectric element unit 13 may include a fourth transparent substrate 103, a fourth transparent conductor film 203, a fourth n-type oxide semiconductor film 303, and a fourth p-type nickel oxide film 403.
The first to fourth transparent photoelectric element units 10 to 13 may be connected in series to each other. At this time, the first p-type nickel oxide film 400 of the first transparent photoelectric element unit 10 and the second transparent conductor film 201 of the second transparent photoelectric element unit 11 may be connected to each other by a first bonding wire 600.
Similarly, the third p-type nickel oxide film 402 of the third transparent photoelectric element unit 12 and the first transparent conductive film 200 of the first transparent photoelectric element unit 10 may connected to each other by a third bonding wire 602.
The second p-type nickel oxide film 401 of the second transparent photoelectric element unit 11 and the fourth transparent conductor film 203 of the fourth transparent photoelectric element unit 13 may connected to each other by a second bonding wire 601.
The fourth bonding wire 603 may mutually connect the third transparent conductive film 202 of the third transparent photoelectric element unit 12 and the (−) electrode, and the fifth bonding wire 604 may mutually connect the−fourth p-type nickel oxide film 403 of the fourth transparent photoelectric element unit 13 and the (+) electrode. At this time, the fourth bonding wire 603 and the fifth bonding wire 604 may be omitted.
As illustrated in
At this time, the first p-type nickel oxide film 400 of the first transparent photoelectric element unit 10 and the second p-type nickel oxide film 401 of the second transparent photoelectric element unit 11 may be connected to each other by the first bonding wire 600.
Further, the second transparent conductive film 201 of the second transparent photoelectric element unit 11 and the fourth p-type nickel oxide film 403 of the fourth transparent photoelectric element unit 13 may be connected to each other by the second bonding wire 601. Furthermore, the fifth bonding wire 604 may mutually connect the fourth transparent conductive film 203 of the fourth transparent photoelectric element unit 13 and the (+) electrode.
Referring to
The transmittance of the transparent photoelectric element module of the second example was measured.
Further, in order to investigate the performance of the photoelectric element unit of the second example before the series connection, ultraviolet ray (λ=365 nm, 10 mW/cm2) was applied to the photoelectric element unit of the second example before the series connection or the parallel connection.
Referring to
In this way, the transparent photoelectric element of the second example of the present invention is a transparent solar cell module, which may be used as a power generation solar cell installed in a window of a building or a vehicle, a glass cover of a mobile phone or the like.
Referring to
The energy band edge illustrated in
The NiO film forms a potential barrier of 0.8 eV of ZnO film as the NiO film and the ZnO film are bonded (
Ultraviolet-reactive ZnO/NiO heterojunction induces field ionization to separate excitons of free carriers. At this time, the NiO film may actively collect the holes.
On the other hand, the transparent conductive film 200 allows for high Voc during operation of the solar cell, which is capable of drawing electrons. That is, although the separated free electrons are difficult to move to the NiO film due to the existence of the potential barrier, since the free electrons easily search for a lower energy level, they move to the transparent conductive film 200. At this time, the discrete energy level of the NiO film accelerates the hole movement and may cause a very rapid instantaneous reaction. Accordingly, the transparent photoelectric element according to some embodiments of the present invention can have high transmittance and rapid photoresponse.
In order to investigate the crystalline quality and the exciton structure, photoluminescence (PL) of the ZnO/NiO heterojunction was measured at room temperature with a laser of 355 nm and was recorded as a reflection mode.
Referring to
In the high energy region, free exciton (FX) markedly appears and exhibits a strong FXn=1 peak at 3.351 eV. The first excited-state emission exciton is clearly observed at FXn=2=3.423 eV. In addition to such a peak, the higher energy region of D0X also exhibits some hills due to recombination of donor-like surface excitons (SX) at 3.315 eV.
Considering the exciton binding energy (60 meV) of ZnO, the exciton easily remains at room temperature. The longitudinal optical (LO) phonon duplicate line of dominant D0X emission shows a regular array shape. Replicated lines of the primary (1LO), secondary (2LO) and tertiary (3LO) of D0X emissions move in the direction of lower energy by about 72 meV from the main D0X emission. The location of the PL peak may be evidence of a high-quality ZnO film or one-dimensional nanostructure at low temperature measurement conditions. Polycrystalline ZnO obviously provides a PL peak at room temperature. Due to the quantum dot structure of NiO, the NiO film may act as a surface protective film of the ZnO film. As a result, a clear P1 peak is induced at room temperature, and it is possible to demonstrate the reduced surface states according to the formation of the ZnO/NiO surface.
While the present invention has been particularly illustrated and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and detail may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. The exemplary embodiments should be considered in a descriptive sense only and not for purposes of limitation.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2016-0164143 | Dec 2016 | KR | national |
