NL2024408B1 - Transparent conductive oxide on a substrate - Google Patents
Transparent conductive oxide on a substrate Download PDFInfo
- Publication number
- NL2024408B1 NL2024408B1 NL2024408A NL2024408A NL2024408B1 NL 2024408 B1 NL2024408 B1 NL 2024408B1 NL 2024408 A NL2024408 A NL 2024408A NL 2024408 A NL2024408 A NL 2024408A NL 2024408 B1 NL2024408 B1 NL 2024408B1
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- Netherlands
- Prior art keywords
- transparent conductive
- conductive oxide
- substrate
- doped
- perovskite structure
- Prior art date
Links
- 239000000758 substrate Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000005693 optoelectronics Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- 239000000463 material Substances 0.000 claims description 33
- 238000005240 physical vapour deposition Methods 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 abstract description 2
- 238000002834 transmittance Methods 0.000 description 8
- 230000005611 electricity Effects 0.000 description 6
- 229910002929 BaSnO3 Inorganic materials 0.000 description 5
- 239000006096 absorbing agent Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052688 Gadolinium Inorganic materials 0.000 description 1
- 244000191761 Sida cordifolia Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000012707 chemical precursor Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 238000001962 electrophoresis Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 230000005525 hole transport Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 238000011002 quantification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022466—Electrodes made of transparent conductive layers, e.g. TCO, ITO layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1884—Manufacture of transparent electrodes, e.g. TCO, ITO
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/36—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the electrodes
- H01L33/40—Materials therefor
- H01L33/42—Transparent materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
In accordance with the present invention there is provided a method for producing a transparent conductive oxide on a substrate. There is also provided a transparent conductive oxide obtainable by the method described herein. In addition, there is provided a solar cell comprising a transparent conductive oxide as described herein. Furthermore, the use of a transparent conductive oxide according to the invention in an optoelectronic device is provided. The present invention provides means to use doped BaSnOg as transparent conductive oxide for various applications, by enabling it to be applied on arbitrary substrates. Furthermore, the transparent conductive oxide has favorable optical properties, such as transparency in the IR region.
Description
P125090NL00 Title: Transparent conductive oxide on a substrate
BACKGROUND OF THE INVENTION The invention is in the field of optoelectronic devices and the like. In particular the present invention is directed to transparent conductive oxides (TCOs), a method for producing TCOs, and the use thereof.
In the field of optoelectronic devices, transparent conductive oxides can be used in many different applications, such as solar cells, light emitting diodes (LEDs), and transparent transistors. Currently available transparent conductive oxides (TCOs) are typically based on zinc oxide, tin oxide and/or indium oxide. The material that is currently used the most is indium tin oxide. However, indium resources are scarce, and prices for indium are high. Another drawback of the currently available TCOs is that although they have a transparency window in the visible part of the electromagnetic spectrum, transmittance in the infrared (IR) is typically low due to fundamental physical limitations, specifically due to free carrier absorption.
Solar cells are becoming increasingly important as a source for renewable energy, and as an alternative for fossil fuels for generating electricity. In order to make efficient use of the entire solar spectrum, multi- junction or tandem solar cells have been developed, which enable electricity generation from photons of several different wavelengths. A significant part of the photons from the sun that reach the earth’s surface have energy levels in the IR region. However, using the currently available TCOs, these photons can not be used for generating electricity, because they are absorbed in the TCO.
Other applications that would benefit from TCOs with a broader transparency window include light emitting diodes (LEDs) and transparent transistors.
Therefore, other materials are studied for their applicability as TCO. Promising candidates for this application are doped BaSn0: (BSO) materials.
Lanthanum-doped BSO materials are disclosed in US201548282.
These materials show a combination of conductivity and a degree of transparency in the visible region of the electromagnetic spectrum.
However, in order to obtain films of these materials with acceptable conductivity, the materials need to be deposited on a substrate having perovskite (ABOs3) structure with a specific lattice constant.
In order for practical applicability in devices, however, it is required that films of TCO material can be deposited on various substrates, including amorphous substrates, while maintaining good conductivity and transparency.
An object of the present invention is to overcome one or more problems of the known TCO materials.
Another object of the invention is to enable the deposition of doped BSO materials on arbitrary substrates.
Another object of the invention is to provide a transparent conductive oxide material with improved transparency in the infrared (IR) region, while maintaining transparency in the visible region of the electromagnetic spectrum.
BRIEF SUMMARY OF THE INVENTION In accordance with the present invention there is provided a method for producing a transparent conductive oxide on a substrate. There is also provided a transparent conductive oxide obtainable by the method described herein. In addition, there is provided a solar cell comprising a transparent conductive oxide as described herein.
Furthermore, the use of a transparent conductive oxide according to the invention in an optoelectronic device is provided. The present invention provides means to use doped BaSnO; as transparent conductive oxide for various applications, by enabling it to be applied on arbitrary substrates. Furthermore, the transparent conductive oxide has favorable optical properties, such as transparency in the IR region.
BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic representation of a transparent conductive oxide according to the invention. Figure 2 is a schematic representation of a solar cell according to an embodiment of the invention. Figure 3 is a graph showing increased crystallinity of doped BaSnO; when applied on a buffer layer according to the invention. Figure 4 1s a graph showing transmittance in the visible and infrared region of a transparent conductive oxide according to the invention.
DETAILED DESCRIPTION OF THE INVENTION According to the invention there is provided a method for producing a transparent conductive oxide on a substrate, comprising the steps of: a) providing a substrate; b) applying a buffer layer comprising a material with layered perovskite structure onto the substrate; c) applying doped BaSnOs onto said layer; wherein the material with layered perovskite structure has a lattice constant of 0.37 to 0.45 nm.
There 1s also provided a transparent conductive oxide obtainable by the method described herein.
Figure 1 is a schematic representation of a transparent conductive oxide according to the invention. Substrate (1), buffer layer comprising a material with layered perovskite structure (2) and doped BaSnO0: (3) are shown.
Surprisingly, according to the present invention, this method results in a transparent conductive oxide with low resistivity, irrespective of the used substrate, while maintaining transparency in the IR region and low resistivity.
A wide range of crystalline and amorphous substrates may be used. Preferably, the substrate is an amorphous substrate, such as glass. This enables application of the TCO in many applications, because there is no need for special and/or expensive substrates.
ABXs3 structure, also known as perovskite structure, refers to lattice structures with general formula ABX3, wherein A and B are cations of different size and X is an anion.
The buffer layer comprises a material with layered perovskite structure. Layered perovskite structure refers to a structure that is built up of one or more 2-dimensional sheets having perovskite structure, resulting in a formula A -1BaX3n+1, wherein n is the number of octahedral layers in a 2-dimensional sheet. The buffer layer may be applied using solution-based or vacuum-based methods available in the art. Preferably, the material with layered perovskite structure is applied by Langmuir-Blodgett deposition.
Other methods include spin-coating, electrophoresis, inkjet printing.
Preferably, the buffer layer promotes strong out-of-plane orientation in the doped BaSnO:; that is applied onto the buffer layer. This may be achieved by choosing a material with layered perovskite structure that exhibits strong preferential orientation, and/or which has a lattice constant close to the lattice constant of the doped BaSn0:. In case of La- doped BaSnO3, the lattice constant a. = 4.12 A. Preferably, the material with layered perovskite structure is Ca2Nb3019, which has a lattice constant a. of 3.86 A. It 1s further preferred that the buffer layer exhibits a high coverage of the surface of the substrate. 5 The material with layered perovskite structure may be applied as a layer with a thickness of several 2-dimensional sheets, such as 1-3 sheets. In addition to the material with layered perovskite structure, the buffer layer may also comprise other materials, for example doped BaSnOs, undoped BaSnO3 and/or other oxides.
The BSO may be doped with La, Sb, Gd or H. Preferably, the BSO is doped with La. The doped BaSnO3; material can be described with general chemical formula BaLa.xSnOg, wherein 0 <x < 0.1.
Application of the doped BSO layer may be performed using physical vapor deposition techniques such as Pulsed Laser Deposition or magnetron sputtering, and/or using chemical vapor deposition techniques. Preferably, the doped BSO is applied using physical vapor deposition as these techniques are compatible with current industrial process flows and do not require chemical precursors.
Generally, it is preferable that the resistivity of the TCO material is as low as possible. Preferably, the TCO has a resistivity of 1x10-2 Qcm or less, more preferably 1x10-3 cm or less, even more preferably 5<10-4 Qem or less, such as 1x104 Qcm or less. Without wishing to be bound by theory, it is believed that the resistivity of the TCOs made with the method as described herein are low, because of the high degree of crystallinity of the doped BaSnOj; thin films..
The doped BaSnOs may be applied as a layer with a thickness of 10-1000 nm, preferably 20-500 nm, such as 50-200 nm.
Preferably, the transparent conductive oxide is transparent for both visible light and infrared light, i.e., light with a wavelength of 800-1200 nm. For quantification of the transparency in the IR region, the transmittance at a wavelength of e.g. 1000 nm can be used. For application of the TCO in optoelectronic devices which require transparency in the IR region, it is preferred that a large fraction of IR radiation is transmitted by the TCO material. Preferably, the TCO has a transmittance of 70% or higher at a wavelength of 1000 nm, more preferably of 80% or higher, such as 90% or higher. Because the transmittance is dependent on layer thickness, the thickness of the doped BaSnO; layer may be adjusted in order to obtain the desired transmittance at a wavelength of 1000. In the case of solar cells, good transparency in the IR region means that IR light can be used for generation of electricity.
According to another aspect of the invention, there is provided a solar cell comprising a transparent conductive oxide as described herein.
There is also provided the use of a transparent conductive oxide as described herein in an optoelectronic device. Examples of optoelectronic device include, but are not limited to solar cells, light emitting diodes (LEDs), displays, and transparent transistors.
Figure 2 is a schematic representation of a solar cell according to an embodiment of the present invention, comprising substrate (1), doped BaSn0: (3), electron selective layer (13), absorber (14), hole transport layer (15), and rear electrode (16). Between the substrate (1), and the doped BaSn0:; (3), there is buffer layer comprising a material with layered perovskite structure (2).
The TCO according to the invention may be used as front electrode of a solar cell, as rear electrode, or both.
With reference to figure 2, the TCO according to the invention allows infrared light to reach the absorber, where, depending on the band gap of the absorber, infrared light can be converted into electric energy. If the rear electrode is also transparent for visible and/or infrared light, additional absorber materials can be provided below the rear electrode. In this way, a larger fraction of the solar spectrum, including infrared light, can be used for the generation of electricity.
In the case of solar cells, specifically for perovskite solar cells, the doped BSO material may act as electrode, as electron selective layer (ESL), or both. The ESL plays an important role in solar cells, with regard to surface passivation, and electron extraction in perovskite solar cells, leading to more efficient electricity generation. Generally, it is believed that forthe electron selective layer its conduction band minimum (CBM) and valence band maximum (VBM) of the electron selective layer have to be lower than those of the perovskite absorber. ESLs based on Ti0: are commonly applied in perovskite solar cells. Without wishing to be bound by theory, the inventors believe that the band offsets, i.e., the (positions of CBM and VMB, respectively) of this material make it suitable as electron selective layer. Analogously, the doped BSO may also act as hole selective layer.
Optimization of the properties of the transparent conductive oxide on a substrate, such as thickness of the doped BaSnO3 and amount of dopant introduced in the material, may be required, depending on the desired functionality. For example, in electron selective layers, there typically is a tradeoff between better carrier selectivity, e.g. achievable by a thicker ESL and better carrier extraction, e.g. achievable by a thinner ESL. Similar tradeoffs may apply to other applications as well.
EXAMPLES Example 1.
Two samples of La-doped BaSnO; on a fused silica substrate were prepared. In one sample, doped BaSnO: was applied directly on the substrate, whereas in the other sample the doped BaSnO3 was applied onto a buffer layer according to the invention. An X-ray diffraction pattern of the two samples is shown in figure 3. The increase in intensity of the peak at 44° 26 and the appearance of a smaller peak around 21° 28 indicate a higher degree of crystallinity for the doped BaSnO: applied onto a buffer layer according to the invention (indicated as ‘w/seed layer’ in figure 3). It is believed that the increased crystallinity forms the basis of the enhanced functional properties of the material, e.g. low resistivity. In figure 4, transmittance in the visible and infrared region is shown for the substrate alone, and for the two samples. It can be seen that the transmittance of the two samples is very similar, indicating that the transparency of the doped BaSnO; is not negatively effected by the buffer layer according to the invention.
Claims (12)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2024408A NL2024408B1 (en) | 2019-12-09 | 2019-12-09 | Transparent conductive oxide on a substrate |
| PCT/NL2020/050768 WO2021118347A1 (en) | 2019-12-09 | 2020-12-09 | Transparent conductive oxide on a substrate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL2024408A NL2024408B1 (en) | 2019-12-09 | 2019-12-09 | Transparent conductive oxide on a substrate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| NL2024408B1 true NL2024408B1 (en) | 2021-08-31 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| NL2024408A NL2024408B1 (en) | 2019-12-09 | 2019-12-09 | Transparent conductive oxide on a substrate |
Country Status (2)
| Country | Link |
|---|---|
| NL (1) | NL2024408B1 (en) |
| WO (1) | WO2021118347A1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150048282A1 (en) | 2012-04-05 | 2015-02-19 | Rftron Co., Ltd. | Transparent compound semiconductor and production method therefor |
| US20170271622A1 (en) * | 2016-06-03 | 2017-09-21 | Solar-Tectic, Llc | High efficiency thin film tandem solar cells and other semiconductor devices |
-
2019
- 2019-12-09 NL NL2024408A patent/NL2024408B1/en not_active IP Right Cessation
-
2020
- 2020-12-09 WO PCT/NL2020/050768 patent/WO2021118347A1/en active Application Filing
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20150048282A1 (en) | 2012-04-05 | 2015-02-19 | Rftron Co., Ltd. | Transparent compound semiconductor and production method therefor |
| US20170271622A1 (en) * | 2016-06-03 | 2017-09-21 | Solar-Tectic, Llc | High efficiency thin film tandem solar cells and other semiconductor devices |
Non-Patent Citations (2)
| Title |
|---|
| JAMES K K ET AL: "Structural and optical properties of La-doped BaSnO3thin films grown by PLD", JOURNAL OF PHYSICS AND CHEMISTRY OF SOLIDS, PERGAMON PRESS, LONDON, GB, vol. 76, 14 August 2014 (2014-08-14), pages 64 - 69, XP029018362, ISSN: 0022-3697, DOI: 10.1016/J.JPCS.2014.07.024 * |
| SHIOGAI JUNICHI ET AL: "Improvement of electron mobility in La:BaSnO3thin films by insertion of an atomically flat insulating (Sr,Ba)SnO3buffer layer", AIP ADVANCES, AMERICAN INSTITUTE OF PHYSICS, 2 HUNTINGTON QUADRANGLE, MELVILLE, NY 11747, vol. 6, no. 6, 7 June 2016 (2016-06-07), XP012208241, DOI: 10.1063/1.4953808 * |
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| WO2021118347A1 (en) | 2021-06-17 |
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