CN101841003B - Double-layer structure deep-ultraviolet transparent conductive film and preparation method thereof - Google Patents
Double-layer structure deep-ultraviolet transparent conductive film and preparation method thereof Download PDFInfo
- Publication number
- CN101841003B CN101841003B CN2010101382221A CN201010138222A CN101841003B CN 101841003 B CN101841003 B CN 101841003B CN 2010101382221 A CN2010101382221 A CN 2010101382221A CN 201010138222 A CN201010138222 A CN 201010138222A CN 101841003 B CN101841003 B CN 101841003B
- Authority
- CN
- China
- Prior art keywords
- sputtering
- transparent conductive
- double
- conductive film
- layer structure
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000004544 sputter deposition Methods 0.000 claims abstract description 61
- 239000000758 substrate Substances 0.000 claims abstract description 54
- 238000002834 transmittance Methods 0.000 claims abstract description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007789 gas Substances 0.000 claims abstract description 13
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 12
- 239000000919 ceramic Substances 0.000 claims abstract description 9
- 229910006404 SnO 2 Inorganic materials 0.000 claims description 9
- 230000003595 spectral effect Effects 0.000 claims description 9
- 230000005540 biological transmission Effects 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000010408 film Substances 0.000 abstract description 68
- 230000003287 optical effect Effects 0.000 abstract description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 abstract description 22
- 238000000034 method Methods 0.000 abstract description 19
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052786 argon Inorganic materials 0.000 abstract description 11
- 239000010409 thin film Substances 0.000 abstract description 11
- 229910003437 indium oxide Inorganic materials 0.000 abstract description 9
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 abstract description 8
- 238000001552 radio frequency sputter deposition Methods 0.000 abstract description 7
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 abstract description 4
- 239000012776 electronic material Substances 0.000 abstract description 2
- 229910005191 Ga 2 O 3 Inorganic materials 0.000 description 26
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000004549 pulsed laser deposition Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 2
- 229910001887 tin oxide Inorganic materials 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009718 spray deposition Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000000233 ultraviolet lithography Methods 0.000 description 1
Images
Landscapes
- Physical Vapour Deposition (AREA)
- Non-Insulated Conductors (AREA)
- Manufacturing Of Electric Cables (AREA)
Abstract
本发明涉及一种锡掺杂氧化铟(ITO)/氧化镓(Ga2O3)双层结构深紫外透明导电膜及其制备方法，属于电子材料技术领域。本发明以紫外光学石英玻璃为基板，用射频磁控溅射Ga2O3陶瓷靶制备Ga2O3层，厚度30-60nm；用直流磁控溅射ITO靶材制备ITO层，厚度15-29nm。溅射气体氩气压强0.2-2Pa，射频溅射功率50-100W，基板温度200-320℃，直流溅射电流80-150mA，直流溅射电压200-400V。所制备的薄膜具有电阻率低、可见光范围透射率高以及紫外和深紫外区域透射率高等优良的光电性能。本发明方法获得的薄膜在紫外光电器件等领域具有良好的应用前景。The invention relates to a tin-doped indium oxide (ITO)/gallium oxide (Ga 2 O 3 ) double-layer structure deep ultraviolet transparent conductive film and a preparation method thereof, belonging to the technical field of electronic materials. The present invention uses ultraviolet optical quartz glass as the substrate, and uses radio frequency magnetron sputtering Ga2O3 ceramic target to prepare Ga2O3 layer with a thickness of 30-60nm ; uses DC magnetron sputtering ITO target to prepare ITO layer with a thickness of 15- 29nm. The argon pressure of the sputtering gas is 0.2-2Pa, the RF sputtering power is 50-100W, the substrate temperature is 200-320°C, the DC sputtering current is 80-150mA, and the DC sputtering voltage is 200-400V. The prepared film has excellent photoelectric properties such as low resistivity, high transmittance in the visible light range, and high transmittance in the ultraviolet and deep ultraviolet regions. The thin film obtained by the method of the invention has good application prospects in the fields of ultraviolet photoelectric devices and the like.
Description
(一)技术领域： (1) Technical field:
本发明涉及一种双层结构深紫外透明导电膜及其制备方法，属于电子材料技术领域。The invention relates to a double-layer structure deep ultraviolet transparent conductive film and a preparation method thereof, belonging to the technical field of electronic materials.
(二)背景技术： (two) background technology:
深紫外发光二极管在高密度光记录、生物与化学传感器的激发光源、安全通信、太空技术、医疗以及高速分解处理公害物质等领域有广泛应用。迄今为止，深紫外线光源以准分子激光和各种倍频激光等气体和固体为媒介的紫外激光和气体灯为主流，存在体积大、寿命短、价格高的缺点，难以实际应用。有机电致发光器件(OLEDs)由于具有高效率、高亮度、宽视角、低功耗、自发光、响应速度快等特点，得到了人们广泛的关注。有机半导体材料通过分子剪裁可调控光电性能，实现深紫外电致发光。有机深紫外发光二极管具有体积小、重量轻、电压低、电流小、亮度高和发光响应速度快等优点，容易与晶体管和集成电路配套使用，便于使用太阳能电池供电，可以在许多领域得到应用。Deep ultraviolet light-emitting diodes are widely used in high-density optical recording, excitation light sources for biological and chemical sensors, security communications, space technology, medical treatment, and high-speed decomposition of public hazards. So far, the mainstream of deep ultraviolet light sources are excimer lasers and various frequency-doubled lasers and other gas and solid-mediated ultraviolet lasers and gas lamps, which have the disadvantages of large size, short life, and high price, making it difficult for practical application. Organic electroluminescent devices (OLEDs) have attracted widespread attention due to their high efficiency, high brightness, wide viewing angle, low power consumption, self-luminescence, and fast response. Organic semiconductor materials can adjust the photoelectric performance through molecular tailoring, and realize deep ultraviolet electroluminescence. Organic deep ultraviolet light-emitting diodes have the advantages of small size, light weight, low voltage, low current, high brightness, and fast luminous response speed. They are easy to be used with transistors and integrated circuits, and are easy to use solar cells for power supply. They can be applied in many fields.
用做有机深紫外发光二极管阳极电极的透明导电膜对有机深紫外发光二极管性能起着关键的作用，透明导电膜肩负电极和透射发射层辐射的深紫外光双重功能。目前研究较多的掺锡的氧化铟(简称ITO)薄膜、掺锑的氧化锡(SnO2:Sb)薄膜、掺氟的氧化锡(SnO2:F)薄膜、掺铝的氧化锌(ZnO:Al)薄膜等透明导电膜的光学带隙一般小于3.7eV，光学透明的波长范围被限制在400-700nm可见光波段，在紫外光区域内是不透明的。深紫外透明导电膜成为制约深紫外有机电致发光器件研究的瓶颈。随着透明光电子学和光电子器件的不断发展，要求透明导电膜的透明区域向深紫外扩展。深紫外透明导电膜在紫外光刻、紫外发光器件、紫外探测器、DNA和高蛋白的分析仪器、紫外固化等众多领域有重要应用，因此制备深紫外透明导电膜具有很大的应用价值。The transparent conductive film used as the anode electrode of the organic deep ultraviolet light-emitting diode plays a key role in the performance of the organic deep ultraviolet light-emitting diode. The transparent conductive film shoulders the dual functions of the electrode and the deep ultraviolet light radiated by the transmission emitting layer. At present, tin-doped indium oxide (ITO) films, antimony-doped tin oxide (SnO 2 :Sb) films, fluorine-doped tin oxide (SnO 2 :F) films, aluminum-doped zinc oxide (ZnO: The optical bandgap of transparent conductive films such as Al) thin films is generally less than 3.7eV, and the optically transparent wavelength range is limited to the 400-700nm visible light band, and is opaque in the ultraviolet region. Deep ultraviolet transparent conductive film has become a bottleneck restricting the research of deep ultraviolet organic electroluminescent devices. With the continuous development of transparent optoelectronics and optoelectronic devices, the transparent region of transparent conductive films is required to extend to deep ultraviolet. Deep ultraviolet transparent conductive films have important applications in many fields such as ultraviolet lithography, ultraviolet light-emitting devices, ultraviolet detectors, DNA and high-protein analysis instruments, and ultraviolet curing. Therefore, the preparation of deep ultraviolet transparent conductive films has great application value.
Ga2O3是一种宽禁带的深紫外透明半导体氧化物，禁带宽度4.8-5.1eV，对应吸收边位于240nm-280nm，为直接带隙的半导体材料，在紫外光区的透过率达到80％以上，弥补了传统的透明导电膜在深紫外区域不透明的缺点，Ga2O3是一种很有潜力的深紫外透明导电材料。近年来，对Ga2O3基透明导电膜的研究主要集中在通过阳离子替位掺杂来提高其光电性能，研究较多的是Sn4+替位Ga3+形成的Sn掺杂β-Ga2O3薄膜。制备Sn掺杂β-Ga2O3薄膜的方法有脉冲激光沉积(Pulsed laser deposition)法，参见Masahiro Orita等人的“低温制备高导电、深紫外透明β-Ga2O3薄膜”，《固体薄膜》411(2002)134-139(Masahiro Orita，Hidenori Hiramatsu，Hiromichi Ohta，et al.Preparation of highly conductive，deepultraviolet transparent β-Ga2O3 thin film at low deposition temperatures，Thin SolidFilms 411(2002)134-139)。脉冲激光沉积法制备的Sn掺杂β-Ga2O3薄膜电导率8.2S.cm-1(电阻率0.12Ω.cm)，薄膜沉积衬底温度380-435℃。脉冲激光沉积法设备昂贵，难以大面积成膜；用脉冲激光沉积法制备的Sn掺杂β-Ga2O3薄膜电阻过高，距离实际的商业应用还有很大距离。因此，有必要研究一种新型的深紫外透明导电膜。Ga 2 O 3 is a deep ultraviolet transparent semiconductor oxide with a wide bandgap. The bandgap width is 4.8-5.1eV, and the corresponding absorption edge is located at 240nm-280nm. It is a semiconductor material with a direct bandgap. The transmittance in the ultraviolet region Reaching more than 80%, it makes up for the shortcomings of traditional transparent conductive films that are opaque in the deep ultraviolet region. Ga 2 O 3 is a very potential deep ultraviolet transparent conductive material. In recent years, the research on Ga 2 O 3 -based transparent conductive films has mainly focused on improving its photoelectric performance through cation substitution doping, and more research is on Sn-doped β-Ga formed by Sn 4+ replacing Ga 3+ 2 O 3 film. The method of preparing Sn-doped β-Ga 2 O 3 thin film includes pulsed laser deposition (Pulsed laser deposition) method . Thin Films》411(2002)134-139(Masahiro Orita, Hidenori Hiramatsu, Hiromichi Ohta, et al.Preparation of highly conductive, deep ultraviolet transparent β-Ga 2 O 3 thin film at low deposition temperatures, Thin SolidFilms 411(2002)134- 139). The electrical conductivity of the Sn-doped β-Ga 2 O 3 film prepared by the pulse laser deposition method is 8.2S.cm -1 (the resistivity is 0.12Ω.cm), and the film deposition substrate temperature is 380-435°C. The equipment of pulsed laser deposition method is expensive, and it is difficult to form large-scale films; the resistance of Sn-doped β-Ga 2 O 3 thin films prepared by pulsed laser deposition method is too high, and there is still a long way to go for practical commercial applications. Therefore, it is necessary to study a new type of deep ultraviolet transparent conductive film.
(三)发明内容： (3) Contents of the invention:
本发明的目的在于提供一种具有工业生产性、工艺稳定性好的一种锡掺杂氧化铟(ITO)/氧化镓(Ga2O3)双层结构深紫外透明导电膜及其制备方法，使其工艺简单、成本低廉、便于大面积成膜，所制成的透明导电膜在可见至深紫外光区域透明性好，电学性能优于Sn掺杂β-Ga2O3薄膜，光电性能稳定。The object of the present invention is to provide a kind of tin-doped indium oxide (ITO)/gallium oxide (Ga 2 O 3 ) double-layer structure deep ultraviolet transparent conductive film with industrial productivity and good process stability and its preparation method. The process is simple, the cost is low, and it is easy to form a large-area film. The transparent conductive film produced has good transparency in the visible to deep ultraviolet region, and its electrical performance is better than that of Sn-doped β-Ga 2 O 3 film, and its photoelectric performance is stable. .
本发明提出一种双层结构深紫外透明导电膜，该透明导电膜由锡掺杂氧化铟(ITO)/氧化镓(Ga2O3)两层组成，其中ITO层厚度15-29nm，优选22nm；Ga2O3层厚度30-60nm，优选50nm。紫外光学石英玻璃选用JGS1远紫外光学石英玻璃或JGS2紫外光学石英玻璃。The present invention proposes a double-layer structure deep ultraviolet transparent conductive film, which is composed of two layers of tin-doped indium oxide (ITO)/gallium oxide (Ga 2 O 3 ), wherein the thickness of the ITO layer is 15-29nm, preferably 22nm ; Ga 2 O 3 layer thickness 30-60nm, preferably 50nm. The ultraviolet optical quartz glass is selected from JGS1 far ultraviolet optical quartz glass or JGS2 ultraviolet optical quartz glass.
本发明提出的制备双层结构锡掺杂氧化铟(ITO)/氧化镓(Ga2O3)深紫外透明导电膜的制备方法是利用现有技术的射频磁控溅射和直流磁控溅射相结合的方法制备双层结构锡掺杂氧化铟(ITO)/氧化镓(Ga2O3)深紫外透明导电膜。本发明的制备是以氧化镓陶瓷靶和锡掺杂氧化铟靶为靶材，Ga2O3陶瓷靶纯度99.99wt％，ITO靶材中SnO2/(In2O3+SnO2)的比例为10wt％。以JGS1远紫外光学石英玻璃或JGS2紫外光学石英玻璃为基板，基板用丙酮、酒精和去离子水超声波清洗，用氮气枪吹干。用机械泵和分子泵对溅射室抽真空，溅射室真空度小于6.0×10-4Pa。调整质量流量计流速和闸板阀开关，向溅射室内充入高纯氩气，使溅射室的氩气压强0.2-2Pa。加热基板，使基板温度200-320℃。开启Ga2O3陶瓷靶的射频电源，预溅射Ga2O3陶瓷靶，射频溅射功率50-100W；待射频辉光放电稳定后，将基板转至Ga2O3靶位对应位置溅射沉积Ga2O3层，厚度30-60nm。开启ITO靶材的直流电源，预溅射ITO靶材，直流溅射电流80-150mA，直流溅射电压200-400V；待直流辉光放电稳定后，将基板转至ITO靶位对应位置溅射沉积ITO层，厚度15-29nm。交替溅射时基板盘转动以保证基板处于不同靶材的相对位置。采用上述方法最后形成双层结构锡掺杂氧化铟(ITO)/氧化镓(Ga2O3)深紫外透明导电膜。The preparation method of the double-layer structure tin-doped indium oxide (ITO)/gallium oxide (Ga 2 O 3 ) deep ultraviolet transparent conductive film proposed by the present invention is to use the radio frequency magnetron sputtering and DC magnetron sputtering in the prior art A combined method is used to prepare a double-layer structure tin-doped indium oxide (ITO)/gallium oxide (Ga 2 O 3 ) deep ultraviolet transparent conductive film. The preparation of the present invention uses gallium oxide ceramic target and tin-doped indium oxide target as target materials, the purity of Ga 2 O 3 ceramic target is 99.99wt%, and the ratio of SnO 2 /(In 2 O 3 +SnO 2 ) in the ITO target is 10wt%. Use JGS1 far-ultraviolet optical quartz glass or JGS2 ultraviolet optical quartz glass as the substrate, clean the substrate ultrasonically with acetone, alcohol and deionized water, and dry it with a nitrogen gun. Vacuumize the sputtering chamber with a mechanical pump and a molecular pump, and the vacuum degree of the sputtering chamber is less than 6.0×10 -4 Pa. Adjust the flow rate of the mass flow meter and the gate valve switch, and fill the sputtering chamber with high-purity argon gas so that the argon pressure in the sputtering chamber is 0.2-2Pa. Heat the substrate to make the substrate temperature 200-320°C. Turn on the RF power of the Ga 2 O 3 ceramic target, pre-sputter the Ga 2 O 3 ceramic target, and the RF sputtering power is 50-100W; after the RF glow discharge is stable, transfer the substrate to the corresponding position of the Ga 2 O 3 target for sputtering Spray deposition Ga 2 O 3 layer, thickness 30-60nm. Turn on the DC power supply of the ITO target, pre-sputter the ITO target, the DC sputtering current is 80-150mA, and the DC sputtering voltage is 200-400V; after the DC glow discharge is stable, turn the substrate to the corresponding position of the ITO target for sputtering Deposit an ITO layer with a thickness of 15-29nm. During alternate sputtering, the substrate disk rotates to ensure that the substrate is in the relative position of different targets. The above method is adopted to finally form a double-layer structure tin-doped indium oxide (ITO)/gallium oxide (Ga 2 O 3 ) deep ultraviolet transparent conductive film.
本发明较好的制备工艺参数如下：The preferred preparation process parameters of the present invention are as follows:
基板温度250-300℃，溅射气体氩气压强0.5-1Pa。射频磁控溅射Ga2O3靶材镀膜时，射频溅射功率60-80W；直流磁控溅射ITO靶材镀膜时，直流溅射电流100-140mA，直流溅射电压280-360V。The substrate temperature is 250-300° C., and the sputtering gas argon pressure is 0.5-1 Pa. When coating the Ga 2 O 3 target by RF magnetron sputtering, the RF sputtering power is 60-80W; when coating the ITO target by DC magnetron sputtering, the DC sputtering current is 100-140mA, and the DC sputtering voltage is 280-360V.
本发明方法制得的双层结构锡掺杂氧化铟(ITO)/氧化镓(Ga2O3)深紫外透明导电膜厚度为45-89nm。可以根据需要，通过控制溅射Ga2O3薄膜和ITO薄膜时间来控制各自的膜厚以及总膜厚。The thickness of the double-layer structure tin-doped indium oxide (ITO)/gallium oxide (Ga 2 O 3 ) deep ultraviolet transparent conductive film prepared by the method of the invention is 45-89 nm. The respective film thicknesses and the total film thickness can be controlled by controlling the sputtering time of the Ga 2 O 3 thin film and the ITO thin film as required.
实验结果表明，本发明制备的ITO/Ga2O3双层薄膜具有Ga2O3薄膜的深紫外透明光学性能和ITO薄膜的良好导电性。在优选工艺条件下，即基板温度250-300℃，溅射气体氩气压强0.5-1Pa；Ga2O3薄膜的制备采用射频磁控溅射纯度99.99％的商品Ga2O3陶瓷靶，溅射功率60-80W，溅射厚度50nm；ITO薄膜的制备采用直流磁控溅射ITO靶，ITO靶材中SnO2/(In2O3+SnO2)的比例为10wt％，直流溅射电流100-140mA，直流溅射电压280-360V，溅射厚度22nm。双层结构22nmITO/50nmGa2O3薄膜光谱透射区域光波长延伸至深紫外光区域(λ＜300nm)，在280nm光学透过率(不含基板)为77.6％，在300nm光学透过率(不含基板)为90.4％，在300-800nm光谱范围平均透过率(不含基板)高于88％，薄膜面电阻为323Ω，薄膜电阻率为2.32×10-3Ω.cm。本发明方法具有工业生产前景，工艺成本低，性能稳定，便于大面积成膜。本发明制备的深紫外透明导电膜在紫外光电器件中具有潜在的应用价值，在拓展太阳能电池窗口电极对紫外光波段和深紫外光波段的有效利用方面具有良好的应用前景。The experimental results show that the ITO/Ga 2 O 3 double-layer film prepared by the present invention has the deep ultraviolet transparent optical properties of the Ga 2 O 3 film and the good conductivity of the ITO film. Under the optimal process conditions, that is, the substrate temperature is 250-300°C, and the sputtering gas argon pressure is 0.5-1Pa; the Ga 2 O 3 thin film is prepared by radio frequency magnetron sputtering with a commercial Ga 2 O 3 ceramic target with a purity of 99.99%. Sputtering power 60-80W, sputtering thickness 50nm; ITO thin film preparation adopts DC magnetron sputtering ITO target, the ratio of SnO 2 /(In 2 O 3 +SnO 2 ) in the ITO target is 10wt%, DC sputtering current 100-140mA, DC sputtering voltage 280-360V, sputtering thickness 22nm. The double-layer structure 22nmITO/50nmGa 2 O 3 thin film spectrum transmission region light wavelength extends to the deep ultraviolet light region (λ<300nm), the optical transmittance at 280nm (without substrate) is 77.6%, and the optical transmittance at 300nm (without Including the substrate) is 90.4%, the average transmittance (excluding the substrate) in the 300-800nm spectral range is higher than 88%, the film surface resistance is 323Ω, and the film resistivity is 2.32×10 -3 Ω.cm. The method of the invention has industrial production prospects, low process cost, stable performance and is convenient for large-area film formation. The deep ultraviolet transparent conductive film prepared by the invention has potential application value in ultraviolet photoelectric devices, and has good application prospects in expanding the effective utilization of solar cell window electrodes to ultraviolet light bands and deep ultraviolet light bands.
(四)附图说明： (4) Description of drawings:
图1实施例1中溅射制备的双层结构22nmITO/50nmGa2O3薄膜在200-800nm范围的透过率曲线。Fig. 1 is the transmittance curve in the range of 200-800nm of the double-layer structure 22nm ITO/50nmGa 2 O 3 film prepared by sputtering in Example 1.
图2实施例2中溅射制备的双层结构22nmITO/40nmGa2O3薄膜在200-800nm范围的透过率曲线。Fig. 2 is the transmittance curve in the range of 200-800nm of the double-layer structure 22nm ITO/40nmGa 2 O 3 film prepared by sputtering in Example 2.
图3实施例3中溅射制备的双层结构29nmITO/50nmGa2O3薄膜在200-800nm范围的透过率曲线。Fig. 3 is the transmittance curve in the range of 200-800nm of the double-layer structure 29nm ITO/50nmGa 2 O 3 film prepared by sputtering in Example 3.
图4实施例4中溅射制备的双层结构22nmITO/60nmGa2O3薄膜在200-800nm范围的透过率曲线。Fig. 4 is the transmittance curve in the range of 200-800nm of the double-layer structure 22nm ITO/60nmGa 2 O 3 film prepared by sputtering in Example 4.
图5实施例5中溅射制备的双层结构15nmITO/50nmGa2O3薄膜在200-800nm范围的透过率曲线。Fig. 5 is the transmittance curve in the range of 200-800nm of the double-layer structure 15nm ITO/50nmGa 2 O 3 film prepared by sputtering in Example 5.
图6实施例6中溅射制备的双层结构22nmITO/30nmGa2O3薄膜在200-800nn范围的透过率曲线。Fig. 6 is the transmittance curve in the range of 200-800nm of the double-layer structure 22nm ITO/30nmGa 2 O 3 film prepared by sputtering in Example 6.
(五)具体实施方式：下面对本发明的具体实施方式作详细说明：(5) specific embodiment: the specific embodiment of the present invention is described in detail below:
实施例1：22nmITO/50nmGa2O3 Example 1: 22nmITO/ 50nmGa2O3
基板选用JGS1远紫外光学石英玻璃，用丙酮、酒精和去离子水超声波清洗基板，用氮气枪吹干。将纯度99.99wt％的Ga2O3陶瓷靶安装在磁控溅射室中的一个射频阴极靶槽中，将SnO2/(In2O3+SnO2)比例为10wt％的ITO靶材安装在磁控溅射室中的一个直流阴极靶槽中。将清洗过的JGS1远紫外光学石英玻璃放入衬底架，把衬底架插入溅射室中的衬底盘中。用机械泵和分子泵对溅射室抽真空，使溅射室真空度小于6.0×10-4Pa。设置温度控制器，调节加热电流加热基板，使基板温度稳定在250℃。调整质量流量计流速和闸板阀开关，向溅射室内充入纯度99.99％的氩气，使溅射室的氩气压强0.5Pa；开启Ga2O3陶瓷靶的射频电源，预溅射Ga2O3陶瓷靶，射频溅射功率70W，待射频辉光放电稳定后，将基板转至Ga2O3靶位对应位置溅射沉积Ga2O3层，厚度50nm。开启ITO靶材的直流电源，预溅射ITO靶材，直流溅射电流120mA，直流溅射电压320V，待直流辉光放电稳定后，将基板转至ITO靶位对应位置溅射沉积ITO层，厚度22nm。交替溅射时衬底盘转动以保证基板处于不同靶材的相对位置。采用上述方法最后形成双层结构22nmITO/50nmGa2O3深紫外透明导电膜。所制备的双层结构22nmITO/50nmGa2O3深紫外透明导电膜在200-800nm范围的透过率曲线如图1所示。在280nm光学透过率(不含基板)为77.6％，在300nm光学透过率(不含基板)为90.4％，在300-800nm光谱范围平均透过率(不含基板)高于88％，薄膜面电阻为323Ω，薄膜电阻率为2.32×10-3Ω.cm。The substrate is made of JGS1 far-ultraviolet optical quartz glass. The substrate is ultrasonically cleaned with acetone, alcohol and deionized water, and dried with a nitrogen gun. A Ga 2 O 3 ceramic target with a purity of 99.99 wt% was installed in a radio frequency cathode target slot in a magnetron sputtering chamber, and an ITO target with a SnO 2 /(In 2 O 3 +SnO 2 ) ratio of 10 wt% was installed In a DC cathode target slot in a magnetron sputtering chamber. Put the cleaned JGS1 far-ultraviolet optical quartz glass into the substrate holder, and insert the substrate holder into the substrate tray in the sputtering chamber. Vacuum the sputtering chamber with a mechanical pump and a molecular pump, so that the vacuum degree of the sputtering chamber is less than 6.0×10 -4 Pa. Set the temperature controller, adjust the heating current to heat the substrate, and stabilize the substrate temperature at 250°C. Adjust the flow rate of the mass flow meter and the gate valve switch, fill the sputtering chamber with argon gas with a purity of 99.99%, so that the argon pressure in the sputtering chamber is 0.5 Pa; turn on the RF power supply of the Ga2O3 ceramic target, and pre-sputter Ga 2 O 3 ceramic target, radio frequency sputtering power 70W, after the radio frequency glow discharge is stable, transfer the substrate to the corresponding position of the Ga 2 O 3 target to sputter and deposit a Ga 2 O 3 layer with a thickness of 50nm. Turn on the DC power supply of the ITO target, pre-sputter the ITO target, the DC sputtering current is 120mA, and the DC sputtering voltage is 320V. After the DC glow discharge is stable, turn the substrate to the corresponding position of the ITO target to sputter and deposit the ITO layer. Thickness 22nm. During alternate sputtering, the substrate disk rotates to ensure that the substrate is in the relative position of different targets. The above method is adopted to finally form a double-layer structure 22nmITO/50nmGa 2 O 3 deep ultraviolet transparent conductive film. The transmittance curve of the prepared double-layer structure 22nmITO/50nmGa 2 O 3 deep ultraviolet transparent conductive film in the range of 200-800nm is shown in FIG. 1 . The optical transmittance (excluding substrate) at 280nm is 77.6%, the optical transmittance at 300nm (excluding substrate) is 90.4%, and the average transmittance (excluding substrate) in the 300-800nm spectral range is higher than 88%. The surface resistance of the film is 323Ω, and the resistivity of the film is 2.32×10 -3 Ω.cm.
实施例2：22nmITO/40nmGa2O3 Example 2 : 22nmITO/ 40nmGa2O3
制备工艺同实施例1，所不同的是射频溅射沉积Ga2O3层厚度40nm。采用上述工艺最后形成双层结构22nmITO/40nmGa2O3深紫外透明导电膜。所制备的双层结构22nmITO/40nmGa2O3深紫外透明导电膜在200-800nm范围的透过率曲线如图2所示。在280nm光学透过率(不含基板)为75.8％，在300nm光学透过率(不含基板)为82.6％，在300-800nm光谱范围平均透过率(不含基板)高于86％，薄膜面电阻为334Ω，薄膜电阻率为2.07×10-3Ω.cm。The preparation process is the same as in Example 1, except that the Ga 2 O 3 layer is deposited by radio frequency sputtering with a thickness of 40 nm. The above-mentioned process is finally used to form a double-layer structure 22nmITO/40nmGa 2 O 3 deep ultraviolet transparent conductive film. The transmittance curve of the prepared double-layer structure 22nmITO/40nmGa 2 O 3 deep ultraviolet transparent conductive film in the range of 200-800nm is shown in FIG. 2 . The optical transmittance (excluding substrate) at 280nm is 75.8%, the optical transmittance at 300nm (excluding substrate) is 82.6%, and the average transmittance (excluding substrate) in the 300-800nm spectral range is higher than 86%. The surface resistance of the film is 334Ω, and the resistivity of the film is 2.07×10 -3 Ω.cm.
实施例3：29nmITO/50nmGa2O3 Example 3: 29nmITO/ 50nmGa2O3
制备工艺同实施例1，所不同的是基板选用JGS2紫外光学石英玻璃，基板温度300℃，溅射气体氩气压强1.0Pa，射频溅射功率60W，直流溅射电流140mA，直流溅射电压360V，溅射沉积ITO层厚度29nm。采用上述工艺最后形成双层结构29nmITO/50nmGa2O3深紫外透明导电膜。所制备的29nmITO/50nm Ga2O3双层结构深紫外透明导电膜在200-800nm范围的透过率曲线如图3所示。在280nm光学透过率(不含基板)为70.9％，在300nm光学透过率(不含基板)为87.5％，在300-800nm光谱范围平均透过率(不含基板)高于88％，薄膜面电阻为262Ω，薄膜电阻率为2.07×10-3Ω.cm。The preparation process is the same as in Example 1, except that the substrate is made of JGS2 ultraviolet optical quartz glass, the substrate temperature is 300°C, the argon pressure of the sputtering gas is 1.0Pa, the RF sputtering power is 60W, the DC sputtering current is 140mA, and the DC sputtering voltage is 360V , sputter-deposited ITO layer thickness 29nm. The above-mentioned process is finally used to form a double-layer structure 29nmITO/50nmGa 2 O 3 deep ultraviolet transparent conductive film. The transmittance curve of the prepared 29nm ITO/50nm Ga 2 O 3 double-layer structure deep ultraviolet transparent conductive film in the range of 200-800nm is shown in FIG. 3 . The optical transmittance (excluding substrate) at 280nm is 70.9%, the optical transmittance at 300nm (excluding substrate) is 87.5%, and the average transmittance (excluding substrate) in the 300-800nm spectral range is higher than 88%. The surface resistance of the film is 262Ω, and the resistivity of the film is 2.07×10 -3 Ω.cm.
实施例4：22nmITO/60nmGa2O3 Example 4: 22nmITO/60nmGa 2 O 3
制备工艺同实施例1，所不同的是基板温度270℃，溅射气体氩气压强0.8Pa，射频溅射功率80W，射频溅射沉积Ga2O3层厚度60nm，直流溅射电流100mA，直流溅射电压280V。采用上述工艺最后形成双层结构22nmITO/60nmGa2O3深紫外透明导电膜。所制备的双层结构22nmITO/60nmGa2O3深紫外透明导电膜在200-800nm范围的透过率曲线如图4所示。在280nm光学透过率(不含基板)为72.4％，在300nm光学透过率(不含基板)为89.7％，在300-800nm光谱范围平均透过率(不含基板)高于88％，薄膜面电阻为335Ω，薄膜电阻率为2.74×10-3Ω.cm。The preparation process is the same as in Example 1, except that the substrate temperature is 270°C, the argon pressure of the sputtering gas is 0.8Pa, the radio frequency sputtering power is 80W, the thickness of the Ga2O3 layer deposited by radio frequency sputtering is 60nm , the DC sputtering current is 100mA, and the DC sputtering current is 100mA. The sputtering voltage is 280V. The above-mentioned process is finally used to form a double-layer structure 22nmITO/60nmGa 2 O 3 deep ultraviolet transparent conductive film. The transmittance curve of the prepared double-layer structure 22nmITO/60nmGa 2 O 3 deep ultraviolet transparent conductive film in the range of 200-800nm is shown in FIG. 4 . The optical transmittance (excluding substrate) at 280nm is 72.4%, the optical transmittance at 300nm (excluding substrate) is 89.7%, and the average transmittance (excluding substrate) in the 300-800nm spectral range is higher than 88%. The surface resistance of the film is 335Ω, and the resistivity of the film is 2.74×10 -3 Ω.cm.
实施例5：15nmITO/50nmGa2O3 Example 5: 15nmITO/ 50nmGa2O3
制备工艺同实施例1，所不同的是基板选用JGS2紫外光学石英玻璃，基板温度200℃，溅射气体氩气压强2.0Pa，射频溅射功率100W，直流溅射电流150mA，直流溅射电压400V，溅射沉积ITO层厚度15nm。采用上述工艺最后形成双层结构15nmITO/50nmGa2O3深紫外透明导电膜。所制备的双层结构15nmITO/50nmGa2O3深紫外透明导电膜在200-800nm范围的透过率曲线如图5所示。在280nm光学透过率(不含基板)为62.4％，在300nm光学透过率(不含基板)为73.8％，在300-800nm光谱范围平均透过率(不含基板)高于80％，薄膜面电阻为1509Ω，薄膜电阻率为9.7×10-3Ω.cm。The preparation process is the same as in Example 1, except that the substrate is made of JGS2 ultraviolet optical quartz glass, the substrate temperature is 200°C, the argon pressure of the sputtering gas is 2.0Pa, the RF sputtering power is 100W, the DC sputtering current is 150mA, and the DC sputtering voltage is 400V , sputter-deposited ITO layer thickness 15nm. The above-mentioned process is finally used to form a double-layer structure 15nmITO/50nmGa 2 O 3 deep ultraviolet transparent conductive film. The transmittance curve of the prepared double-layer structure 15nmITO/50nmGa 2 O 3 deep ultraviolet transparent conductive film in the range of 200-800nm is shown in FIG. 5 . The optical transmittance (excluding substrate) at 280nm is 62.4%, the optical transmittance at 300nm (excluding substrate) is 73.8%, and the average transmittance (excluding substrate) in the 300-800nm spectral range is higher than 80%. The surface resistance of the film is 1509Ω, and the resistivity of the film is 9.7×10 -3 Ω.cm.
实施例6：22nmITO/30nmGa2O3 Example 6: 22nmITO/30nmGa 2 O 3
制备工艺同实施例1，所不同的是基板温度320℃，溅射气体氩气压强0.2Pa，射频溅射功率50W，直流溅射电流80mA，直流溅射电压200V，射频溅射沉积Ga2O3层厚度30nm。采用上述工艺最后形成双层结构22nmITO/30nmGa2O3深紫外透明导电膜。所制备的双层结构22nmITO/30nmGa2O3深紫外透明导电膜在200-800nm范围的透过率曲线如图6所示。在280nm光学透过率(不含基板)为71.1％，在300nm光学透过率(不含基板)为77.4％，在300-800nm光谱范围平均透过率(不含基板)高于86％，薄膜面电阻为330Ω，薄膜电阻率为1.71×10-3Ωcm。The preparation process is the same as in Example 1, the difference is that the substrate temperature is 320°C, the argon pressure of the sputtering gas is 0.2Pa, the RF sputtering power is 50W, the DC sputtering current is 80mA, the DC sputtering voltage is 200V, and Ga 2 O is deposited by RF sputtering. The thickness of the 3 layers is 30nm. The above-mentioned process is finally used to form a double-layer structure 22nmITO/30nmGa 2 O 3 deep ultraviolet transparent conductive film. The transmittance curve of the prepared double-layer structure 22nmITO/30nmGa 2 O 3 deep ultraviolet transparent conductive film in the range of 200-800nm is shown in FIG. 6 . The optical transmittance (excluding substrate) at 280nm is 71.1%, the optical transmittance at 300nm (excluding substrate) is 77.4%, and the average transmittance (excluding substrate) in the 300-800nm spectral range is higher than 86%. The surface resistance of the film was 330Ω, and the resistivity of the film was 1.71×10 -3 Ωcm.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101382221A CN101841003B (en) | 2010-03-30 | 2010-03-30 | Double-layer structure deep-ultraviolet transparent conductive film and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101382221A CN101841003B (en) | 2010-03-30 | 2010-03-30 | Double-layer structure deep-ultraviolet transparent conductive film and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101841003A CN101841003A (en) | 2010-09-22 |
| CN101841003B true CN101841003B (en) | 2012-05-23 |
Family
ID=42744244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101382221A Expired - Fee Related CN101841003B (en) | 2010-03-30 | 2010-03-30 | Double-layer structure deep-ultraviolet transparent conductive film and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101841003B (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102290338B (en) * | 2011-09-15 | 2013-04-10 | 江苏汇景薄膜科技有限公司 | Room-temperature large-area deposition production process for transparent conductive film |
| CN104090433A (en) | 2014-06-19 | 2014-10-08 | 合肥鑫晟光电科技有限公司 | Array substrate and display device |
| CN109136869B (en) * | 2018-07-17 | 2020-07-31 | 中山市华南理工大学现代产业技术研究院 | Metal-doped gallium oxide transparent conductive film for ultraviolet band and preparation method thereof |
| CN108950482A (en) * | 2018-08-23 | 2018-12-07 | 张治国 | A kind of ultraviolet 300nm is semi-transparent-copper and indium doped transparent conductive film and preparation method thereof |
| CN112420888B (en) * | 2021-01-21 | 2021-04-23 | 华灿光电（浙江）有限公司 | Ultraviolet light-emitting diode epitaxial wafer and preparation method thereof |
| JP7257562B2 (en) * | 2021-04-27 | 2023-04-13 | Ｊｘ金属株式会社 | LAMINATED FUNCTION AS TRANSPARENT CONDUCTIVE FILM, METHOD FOR MANUFACTURING SAME, AND OXIDE SPUTTERING TARGET FOR MANUFACTURING SAME LAMINATED PRODUCT |
| WO2022230754A1 (en) * | 2021-04-27 | 2022-11-03 | Ｊｘ金属株式会社 | Layered body having function as transparent electroconductive film and method for producing same, and oxide sputtering target for said layered body production |
| CN113231401A (en) * | 2021-05-14 | 2021-08-10 | 中国科学院上海高等研究院 | Electrostatic dust removal device and camera |
| CN117026159A (en) * | 2023-08-08 | 2023-11-10 | 山东师范大学 | Method for improving mobility of gallium oxide film Hall |
| CN117276403A (en) * | 2023-09-22 | 2023-12-22 | 安徽华晟新能源科技有限公司 | Preparation method of solar cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100813854B1 (en) * | 2007-04-23 | 2008-03-17 | 삼성에스디아이 주식회사 | Organic light emitting device and manufacturing method thereof |
-
2010
- 2010-03-30 CN CN2010101382221A patent/CN101841003B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN101841003A (en) | 2010-09-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101841003B (en) | Double-layer structure deep-ultraviolet transparent conductive film and preparation method thereof | |
| CN105449106B (en) | A kind of transparent electrode and preparation method thereof based on super thin metal | |
| CN105552185B (en) | A kind of full-inorganic light emitting diode with quantum dots and preparation method thereof based on inorganic perovskite material | |
| CN105470400B (en) | A kind of preparation method and application of perovskite film | |
| CN102194956B (en) | Method for evaporating indium tin oxide (ITO) | |
| CN102174689A (en) | FZO/metal/FZO transparent conductive film and preparation method thereof | |
| CN1979695A (en) | Flexible composite transparent conductive film and mfg. method | |
| EP3110770B1 (en) | Coated glazing | |
| CN102054938A (en) | Sandwich anode structure of organic electroluminescent device and preparation method thereof | |
| CN105551579A (en) | Electrochromic multi-layered transparent conductive thin film and preparation method therefor | |
| CN105624625B (en) | A kind of method for improving ZnO/Ag/ZnO transparent conductive film photoelectric properties | |
| CN100565716C (en) | Transparent conductive film and preparation method thereof | |
| CN106119778A (en) | The method of room temperature sputtering sedimentation flexibility AZO transparent conductive film | |
| CN101661810B (en) | Dark purple external amorphous transparent conductive film and preparation method thereof | |
| CN106229424A (en) | A kind of luminescent device based on perovskite thin slice and preparation method thereof | |
| CN101436647B (en) | Vacuum Ultraviolet Electroluminescence Devices Based on ZnO Nanorods/Organic Luminescent Material Composite Layer | |
| CN108914077A (en) | One kind being based on Nb2O5Transparent conductive oxide film and preparation method thereof | |
| CN102051578B (en) | Transparent conductive metallic film and preparation method thereof | |
| CN102509756B (en) | Novel total inorganic oxide quantum dot LED based on FTO, and manufacturing method thereof | |
| CN103117333A (en) | Transparent electrode manufacturing method improving device yield rate | |
| CN111326664A (en) | Quantum dot light emitting diode device and ink for making the same | |
| CN102277570A (en) | Method for preparing ZnO/Cu/ZnO transparent conductive thin film | |
| CN105908127B (en) | A kind of p-type doped tin dioxide transparent conductive film and preparation method thereof | |
| CN105741916B (en) | Flexible transparent electrode and preparation method thereof | |
| CN104993064B (en) | A kind of anti-short-circuit transparent OLED device and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20130330 |