WO2015168881A1

WO2015168881A1 - Novel etching solution used in oxide material system, etching method and application thereof

Info

Publication number: WO2015168881A1
Application number: PCT/CN2014/076956
Authority: WO
Inventors: 范冰丰; 王钢; 童存声
Original assignee: 佛山市中山大学研究院
Priority date: 2014-05-07
Filing date: 2014-05-07
Publication date: 2015-11-12

Abstract

Disclosed in the present invention is a novel etching solution used in an oxide material system. The novel etching solution comprises an oxide etching solution, an adjusting agent having the effect of adjusting thickness, and water. At the same time, also disclosed in the present invention are an etching method and an application of the novel etching solution. The novel etching solution and the etching method disclosed in the present invention are generally suitable for etching oxide thin film materials based on Sn, Zn, Al, Ga and In and alloy thereof, especially suitable for etching oxide materials of ZnO, AZO, GZO, IGZO, IZO, etc., and can also be widely used for etching oxide materials for making fine electronic components, such as semiconductor photoelectric devices, solar cells, TFT film transistors, semiconductor integrated circuits and transparent electrodes, etc. Compared with traditional etching solutions, the novel etching solution of the present invention has the effects of lateral etching inhibition, uneven etching prevention and etching residual prevention.

Description

一种用于氧化物材料体系的新型蚀刻液及其蚀刻方法和应用技术领域 Novel etching liquid for oxide material system and etching method and application thereof

本发明涉及一种适用于氧化物材料体系刻蚀的新型蚀刻液。更具体地，本发明涉及一种适用于 In、 Sn、 Al、 Ga和 Zn等氧化物材料体系刻蚀的蚀刻液和蚀刻方法，其主要用于制备精细电子部件中氧化物材料的刻蚀，例如光电半导体器件、半导体集成电路和透明电极等中的氧化物材料的刻蚀。背景技术 The present invention relates to a novel etching solution suitable for etching an oxide material system. More particularly, the present invention relates to an etching solution and an etching method suitable for etching an oxide material system such as In, Sn, Al, Ga, and Zn, which are mainly used for preparing an etching of an oxide material in a fine electronic component. Etching of an oxide material in, for example, an optoelectronic semiconductor device, a semiconductor integrated circuit, and a transparent electrode. Background technique

透明导电薄膜（Transparent Conductive Oxide, TC0)材料技术是以 ΠΌ、 ∑110、111₂0₃、310₂等透明氧化物半导体材料及上述氧化物的掺杂体系为材料基础，涵盖材料生长、器件制备、装备制造等多领域学科的先端技术，技术领域包括显示、照明、新材料、半导体微加工、新装备、集成电路、 ***集成等诸多技术领域。 The Transparent Conductive Oxide (TC0) material technology is based on the transparent oxide semiconductor materials such as yttrium, lanthanum 110, 111 ₂ 0 ₃ and 310 ₂ and the doping system of the above oxides, covering material growth and device preparation. Advanced technology in many fields such as equipment manufacturing. The technical fields include display, lighting, new materials, semiconductor micromachining, new equipment, integrated circuits, system integration and many other technical fields.

透明导电薄膜材料是新一代光电器件的基础性功能材料，在上世纪末得到高速发展和广泛的应用，约占功能膜的 50%以上，有人称其为 "二十世纪最后的几项大型技术之一"。透明导电薄膜材料以其接近金属的导电率、可见光范围内的高透射比、红外高反射比以及其半导体特性，广泛地应用于太阳能电池、显示器、气敏元件、抗静电涂层以及半导体 /绝缘体 /半导体（SIS)异质结等特性 (文献： Hideo Hosono , " Recent progress in transparent oxide semiconductors: Materials and device application", Thin Solid Films 515 (2007) 6000 - 6014),近年来得以迅速发展，特别是在薄膜晶体管（TFT)制造、平板液晶显示（LCD)、 LED及太阳电池透明电极以及红外辐射反射镜涂层、火车飞机用玻璃除霜、巡航导弹的窗口、建筑物幕墙玻璃等方面获得广泛应用，被誉为第二半导体工业。 Transparent conductive film material is the basic functional material of the new generation of optoelectronic devices. It has been developed rapidly and widely used at the end of the last century, accounting for more than 50% of the functional film. Some people call it "the last few large technologies of the twentieth century." One". Transparent conductive film materials are widely used in solar cells, displays, gas sensors, antistatic coatings, and semiconductors/insulators due to their proximity to metal conductivity, high transmittance in the visible range, high infrared reflectance, and semiconductor properties. /Semiconductor (SIS) heterojunction and other characteristics (literature: Hideo Hosono, "Recent progress in transparent oxide semiconductors: Materials and device application", Thin Solid Films 515 (2007) 6000 - 6014), which has developed rapidly in recent years, especially Widely used in thin-film transistor (TFT) manufacturing, flat panel liquid crystal display (LCD), LED and solar cell transparent electrodes and infrared radiation mirror coating, glass defrosting for train aircraft, cruise missile windows, building curtain wall glass, etc. , known as the second semiconductor industry.

透明导电薄膜材料一个重要应用是作为光电半导体器件的透明电极， Klaus Ellmer在 2012年的 Nature Photonics对 ln₂0₃、 Sn0₂、 ZnO和 Ti0₂透明电极材料的现状和发展做了详细描述（文献： Klaus Ellmer, "Past achievements and future challenges in the development of optically transparent electrodes ", Nature Photonics, 2012, 6， 809-817)。其中 Al、 Ga、 In、 Zn氧化物基透明导电薄膜作为新一代透明导电薄膜，拥有极高的透射率，生长适当厚度的薄膜在可见光范围内透射率高达 90%，同时 ZnO薄膜通过掺杂，调整生长环境，控制退火温度，能使其电阻率达到 10— ³数量级。且氧化锌无毒，对环境友好可持续发展，代表着未来透明导电薄膜的发展趋势，具有广阔的产业化前景。 An important application of transparent conductive film materials is as a transparent electrode for optoelectronic semiconductor devices. Klaus Ellmer's 2012 Nature Photonics describes the current status and development of ln ₂ 0 ₃ , Sn0 ₂ , ZnO and TiO ₂ transparent electrode materials (References) Klaus Ellmer, "Past achievements and future challenges in the development of optically transparent electrodes", Nature Photonics, 2012, 6, 809-817). Among them, the Al, Ga, In, Zn oxide-based transparent conductive film has a very high transmittance as a new generation of transparent conductive film, and the film having the appropriate thickness is up to 90% in the visible light range, and the ZnO film is doped. adjusting growth environment, controlling the annealing temperature, its resistance can be orders of magnitude rate of ^10-3. And zinc oxide is non-toxic, environmentally friendly and sustainable, representing the development trend of transparent conductive films in the future, with broad production. Industrialization prospects.

透明导电薄膜材料另一个重要应用是作为功能材料在电子器件中的应用， Another important application of transparent conductive film materials is the use of functional materials in electronic devices.

Heiko Frenzel在 2010年的 Advanced materials中对 ZnO基金属半导体场效应管以及在透明电路中的应用概况作了详细描述（文献： Heiko Frenzel et al.， " Recent Progress on ZnO- Based Metal-Semiconductor Field-Effect Transistors and Their Application in Transparent Integrated Circuits ", Adv. Mater. , 2010， 22， 5332 - 5349), 在这些器件应用中，由 ZnO基氧化物材料构成的功能薄层器件扮演着重要角色。 Heiko Frenzel's overview of ZnO-based metal-semiconductor FETs and their applications in transparent circuits is detailed in 2010 Advanced Materials (Reference: Heiko Frenzel et al., "Recent Progress on ZnO- Based Metal-Semiconductor Field- Effect Transistors and Their Application in Transparent Integrated Circuits ", Adv. Mater., 2010, 22, 5332 - 5349), in these device applications, functional thin layer devices composed of ZnO-based oxide materials play an important role.

透明导电薄膜材料另一个重要应用是 IGZ0 ( Indium Gallium Zinc Oxide, 即氧化铟镓锌技术） TFT 技术在显示领域的应用， IGZ0-TFT 的这股热潮始于 2003、 2004年日本东京工业大学 Hosono小组相继在 Science和 Nature上报道的关于 IGZ0-TFT 的研究成果（文献 1： Hideo Hosono et al. , "Thin- Film Transistor Fabricated in Single-Crystalline Transparent Oxide Semiconductor", Science 23 May 2003： Vol. 300, no. 5623, pp. 1269—1272; 文献 2： Hideo Hosono et al.， "Room- temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors", Nature 2004, 432， 488-492)。目前，除了美国、台湾、韩国等高等研究机构开展大量的研究外，国际显示巨头也纷纷投入该技术，如夏普率先宣布可实现 IGZ0-TFT量产，三星、 LG和友达光电也在大力开发该面板技术。 Another important application of transparent conductive film materials is the application of IGZ0 (Indium Gallium Zinc Oxide) TFT technology in the field of display. The IGZ0-TFT boom began in 2003 and 2004 at the Hosono Group of Tokyo Institute of Technology, Japan. Research results on IGZ0-TFT reported in Science and Nature (Document 1: Hideo Hosono et al., "Thin-Film Transistor Fabricated in Single-Crystalline Transparent Oxide Semiconductor", Science 23 May 2003: Vol. 300, no 5623, pp. 1269—1272; Document 2: Hideo Hosono et al., "Room-temperature fabrication of transparent flexible thin-film transistors using amorphous oxide semiconductors", Nature 2004, 432, 488-492). At present, in addition to a large number of research institutes such as the United States, Taiwan, South Korea and other high-level research institutions, international display giants have also invested in this technology. For example, Sharp is the first to announce that IGZ0-TFT mass production can be realized. Samsung, LG and AU Optronics are also developing. The panel technology.

虽然，氧化物透明导电薄膜材料已经在诸多领域取得重要应用，比如 Al、 Ga、 Zn、 In基氧化物基透明导电薄膜的电学性能和光学性能已经达到甚至优于 IT0透明导电薄膜，但是与材料研究相比，将氧化物材料及其器件的工艺研究却远远的落在后面，尤其是器件的刻蚀工艺，氧化物材料可以通过干法或湿法工艺进行刻蚀。干法刻蚀采用等离子体刻蚀、载能粒子束轰击等方法可以实现速率可控且各向异性的刻蚀轮廓，而湿法刻蚀又分为化学刻蚀和电化学刻蚀等诸多类型，其中化学刻蚀因具有成本低 (不需要干法刻蚀那样昂贵的等离子设备)、刻蚀速率可控、操作简单以及适用范围广等优点而被广泛采用。尤其是在电子设备的尺寸、重量和功耗的降低已经进步的情况下，透明氧化物半导体和透明导电氧化物在光电半导体器件、显示器领域中等精细电子器件的制备中，湿法刻蚀显得尤为重要。 Although oxide transparent conductive film materials have been used in many fields, such as Al, Ga, Zn, In-based oxide-based transparent conductive films, electrical and optical properties have been achieved or even better than IT0 transparent conductive films, but with materials Compared with the research, the process research of oxide materials and their devices is far behind, especially in the etching process of devices. Oxide materials can be etched by dry or wet processes. Dry etching can achieve a controlled rate and anisotropic etch profile by plasma etching, particle beam bombardment, etc., while wet etching is divided into chemical etching and electrochemical etching. Among them, chemical etching is widely used because of its low cost (expensive plasma equipment that does not require dry etching), controllable etching rate, simple operation, and wide application range. Especially in the case where the reduction in size, weight and power consumption of electronic devices has progressed, transparent oxide semiconductors and transparent conductive oxides are particularly useful in the preparation of medium-fine electronic devices in the field of optoelectronic semiconductor devices and displays. important.

现已公开的氧化物材料的化学刻蚀方法主要集中在各种酸或碱溶液的使用，其氧化物器件工艺尚未成熟，其主要原因是氧化物基透明导电薄膜材料的微加工工艺尚未解决。我们知道， Al、 Ga、 Zn、 In基氧化物是一种两性氧化物，对酸、碱的反应都过于强烈，侧向腐蚀严重，刻蚀速率快，难于控制。比如氧化锌基薄膜湿法刻蚀中侧向刻蚀问题一直是 Al、 Ga、 Zn、 In基氧化物薄膜推广应用的瓶颈。 The chemical etching method of the oxide material which has been disclosed is mainly focused on the use of various acid or alkali solutions, and the oxide device process is not yet mature, and the main reason is that the micro-machining process of the oxide-based transparent conductive film material has not been solved. We know that Al, Ga, Zn, and In-based oxides are amphoteric oxides, which are too strongly reactive to acids and bases, have severe lateral corrosion, and have a fast etching rate and are difficult to control. Such as oxygen The problem of lateral etching in wet etching of zinc-based films has been the bottleneck for the popularization of Al, Ga, Zn, and In-based oxide films.

文献披露， Zn、 Al、 Ga、 In基及其合金氧化物薄膜材料容易被 HC1、 H₃P0₄、 FeCl₃、 TMAH、應 ₄C1、 H 0₃、 ¾P0₄、 ¾P0₄/HAc/¾0、 FeCl₃ · 6¾0等溶液刻蚀（文献 1： H Maki , "Control of surface morphology of ZnO (0001) by hydrochloric acid etching", Thin Solid Films, Volume 411, Issue 1， 22 May 2002, Pages 91 - 95; 文献 2: H. Zheng et al. , "Wet chemical etching of ZnO film using aqueous acidic salt ", Thin Solid Films, Volume 515， Issues 7 - 8, 26 February 2007, Pages 3967-3970；文献 3: Y. C. Lin et al. , "A study on the wet etching behavior of AZ0 (ZnO:Al) transparent conducting film", Applied Surface Science, Volume 254, Issue 9， 28 February 2008, Pages 2671 - 2677；文献 4： Jingchang Sun et al. , "Realization of controllable etching for ZnO film by NH₄C1 aqueous solution and its influence on optical and electrical properties", Applied Surface Science 253 (2007) 5161 - 5165)，甚至是高度稀释的溶液，这会导致刻蚀速率和边缘线轮廓的可控性差。同时， Zn、 Al、 Ga、 In基及其合金氧化物薄膜材料的刻蚀行为还依赖其结晶度、绒面和厚度。因此， Zn、 Al、 Ga、 In基及其合金氧化物薄膜材料要用于器件应用，研究其湿法刻蚀是非常有必要的。 It is disclosed in the literature that Zn, Al, Ga, In and its alloy oxide film materials are easily used by HC1, H ₃ P0 ₄ , FeCl ₃ , TMAH, ₄ C1, H 0 ₃ , 3⁄4P0 ₄ , 3⁄4P0 ₄ /HAc/3⁄40, Solution etching such as FeCl ₃ · 63⁄40 (Document 1: H Maki , "Control of surface morphology of ZnO (0001) by hydrochloric acid etching", Thin Solid Films, Volume 411, Issue 1, 22 May 2002, Pages 91 - 95; Document 2: H. Zheng et al., "Wet chemical etching of ZnO film using aqueous acidic salt", Thin Solid Films, Volume 515, Issues 7 - 8, 26 February 2007, Pages 3967-3970; Document 3: YC Lin et Al. , "A study on the wet etching behavior of AZ0 (ZnO: Al) transparent conducting film", Applied Surface Science, Volume 254, Issue 9, 28 February 2008, Pages 2671 - 2677; Document 4: Jingchang Sun et al. , "Realization of controllable etching for ZnO film by NH ₄ C1 aqueous solution and its influence on optical and electrical properties", Applied Surface Science 253 (2007) 5161 - 5165), even a highly diluted solution, which leads to The etch rate and edge line profile are poorly controllable. At the same time, the etching behavior of Zn, Al, Ga, In and its alloy oxide film materials depends on their crystallinity, suede and thickness. Therefore, Zn, Al, Ga, In and their alloy oxide film materials are used for device applications, and it is very necessary to study wet etching.

进一步的， D. -G. Yoo发表的文献披露了在刻蚀 ZnO基的 0LED器件时，研究了采用 HC1、 HN0₃、 H₂S0₄、 ¾P0₄、 FeCl₃ · 6¾0、 C₂¾0₄等溶液对 ZnO基 0LED 器件中的刻蚀速率 (文献: D. -G. Yoo et al.， "Fabrication of the ZnO thin films using wet-chemical etching processes on application for organic light emitting diode (0LED) devices", Surface & Coatings Technology 202 (2008) 5476 - 5479 )o Further, the literature published by D.-G. Yoo discloses the use of HC1, HN0 ₃ , H ₂ S0 ₄ , 3⁄4P0 ₄ , FeCl ₃ · 63⁄40, C ₂ 3⁄40 _4, etc. when etching ZnO-based OLED devices. The etch rate of the solution in a ZnO-based OLED device (D. -G. Yoo et al., "Fabrication of the ZnO thin films using wet-chemical etching processes on application for organic light emitting diode (0LED) devices", Surface & Coatings Technology 202 (2008) 5476 - 5479 )o

进一步的， J. Tresback发表的文献披露了采用不同浓度的 ¾P0₄溶液对由 n-ZnO/n-Zn。.₉₅Mg。.。₅0/n- Zn。.₉₂Mg。.。₈0构成的 ZnO基外延多层状结构的器件，研究了刻蚀速率等工艺依存性关系（文献： J. Tresback et al.， "Highly Controlled Wet and Dry Etching of Gallium Doped (Mg, Zn) 0 Epi layers Grown Using Metal organic Vapor Phase Epitaxy " , Journal of The Electrochemical Society, 158 (5) H600-H603 (2011) )。 Further, the literature published by J. Tresback discloses the use of different concentrations of 3⁄4P0 ₄ solution pairs from n-ZnO/n-Zn. . ₉₅ Mg. . . . ₅ 0/n- Zn. . ₉₂ Mg. . . . A device of ZnO-based epitaxial multilayer structure composed of ₈₀ , studied the process dependence of etching rate and the like (literature: J. Tresback et al., "Highly Controlled Wet and Dry Etching of Gallium Doped (Mg, Zn) 0 Epi layers Grown Using Metal organic Vapor Phase Epitaxy " , Journal of The Electrochemical Society, 158 (5) H600-H603 (2011) ).

迄今为止，已通过剥离法（lift-off) 法进行了所制备的含有 In、 Ga和 Zn 的氧化物膜、含有 Ga和 Zn的氧化物膜和含有 In和 Zn的氧化物膜的图案化。剥离法公开在 K. Nomura等, Nature, 第 432卷， 2004年 11月 25日，第 488-492页； E. M. C. Fortunato等， Advanced Materials, 2005, 17, No. 5，第 590— 594页； P. Barquinha等， Journal of Non-Crystalline Solid第 352卷，第 9- 20期， 2006，第 1749-1752页等中。 Heretofore, patterning of an oxide film containing In, Ga, and Zn, an oxide film containing Ga and Zn, and an oxide film containing In and Zn has been performed by a lift-off method. The stripping method is disclosed in K. Nomura et al., Nature, Vol. 432, November 25, 2004, pages 488-492; EMC Fortunato et al, Advanced Materials, 2005, 17, No. 5, pages 590-594; P. Barquinha et al, Journal of Non-Crystalline Solid Vol. 352, No. 9-20, 2006, pages 1749-1752, etc.

下面我们对氧化物蚀刻液在专利中的应用情况做进一步描述- 在中国专利申请公开的 201110123598. X中，其采用硫酸氨、硝酸氨或磷酸氨溶液，对本征或掺杂的 Zn0、 ZnMg0、 ZnCd0、 ZnBeO或 ZnCaO薄膜进行腐蚀，形成绒面结构。 In the following, we will further describe the application of the oxide etching solution in the patent - in the Chinese patent application disclosed in 201110123598. X, which uses ammonia sulfate, ammonia nitrate or ammonium phosphate solution, for intrinsic or doped Zn0, ZnMg0, The ZnCd0, ZnBeO or ZnCaO film is etched to form a pile structure.

在中国专利申请公开的 201210165938. X中，其采用弱酸溶液如醋酸、碳酸、氢硫酸、硼酸或氯化物弱酸盐对 ZnO基透明导电薄膜进行湿法刻蚀。 In Chinese Patent Application Publication No. 201210165938.X, a ZnO-based transparent conductive film is wet-etched using a weak acid solution such as acetic acid, carbonic acid, hydrosulfuric acid, boric acid or a weak chloride acid salt.

在中国专利申请公开的 201310295575. 6中，其采用过氧化氢溶液作为刻蚀剂对氧化锌和 /或氧化锌合金进行刻蚀。 In 201310295575. 6 of the Chinese patent application, it is used to etch zinc oxide and/or zinc oxide alloy using a hydrogen peroxide solution as an etchant.

在日本专利申请公开的 No. S58-120780和 S60- 217636和日本专利公开 NO. H04- 5756中，使用硫酸、盐酸、硝酸和氯化铁中的至少一种作为 IT0的湿蚀刻液 (也称作"蚀刻剂"）。在日本专利申请公开 No. 2005- 258115中，使用草酸，磷酸、乙酸和硝酸的混合酸，硝酸铈铵水溶液等作为 IZ0的蚀刻液 (也称作 "蚀刻剂" ) o In the Japanese Patent Application Laid-Open Nos. S58-120780 and S60-217636 and Japanese Patent Publication No. H04-5756, at least one of sulfuric acid, hydrochloric acid, nitric acid and ferric chloride is used as the wet etching solution for IT0 (also called As an "etching agent"). In Japanese Patent Application Laid-Open No. 2005-258115, oxalic acid, a mixed acid of phosphoric acid, acetic acid and nitric acid, an aqueous solution of ammonium cerium nitrate or the like is used as an etching solution for IZ0 (also referred to as "etching agent").

在日本专利申请公开的 JP2008004405- A中，使用含有盐酸的蚀刻液，对添加到氧化锌中含有镁的透明导电膜进行刻蚀，以形成透明电极的透明导电膜进行图案化。 In JP2008004405-A disclosed in Japanese Patent Application, a transparent conductive film containing magnesium added to zinc oxide is etched using an etching solution containing hydrochloric acid to form a transparent conductive film of a transparent electrode.

在韩国专利申请公开的 KR2003001879- A中，使用草酸类化合物、磷酸盐类化合物对铟锌氧化物层进行蚀刻。 In KR2003001879-A disclosed in Korean Patent Application, an indium zinc oxide layer is etched using an oxalic acid compound or a phosphate compound.

在韩国三星公司专利申请公开的 KR20040067013中，采用一种用于除去铟氧化物层的蚀刻剂，包括主氧化剂硫酸，诸如 ¾P0₄、 HN0₃、 C¾C00H、 HC10₄、 H₂0₂ 和混合物 A的辅助氧化剂，含有铵 -基材料的蚀刻抑制剂，及水，其中所述混合物 A 由过一硫酸钾 (2KHS0₅)、硫酸氢钾 ( HS0₄) 和硫酸钾 (K₂S0₄) 按 5： 3： 2的比例混合得到。这种蚀刻剂可以除去铟氧化物层需要去除的部分，而不破坏光阻胶图案或铟氧化物层下面的各层。 In KR20040067013 disclosed in the Korean Patent Application, a etchant for removing an indium oxide layer is used, including a main oxidant sulfuric acid such as 3⁄4P0 ₄ , HN0 ₃ , C3⁄4C00H, HC10 ₄ , H ₂ 0 ₂ and a mixture A. An auxiliary oxidizing agent, an etching inhibitor containing an ammonium-based material, and water, wherein the mixture A is composed of potassium monopersulfate (2KHS0 ₅ ), potassium hydrogen sulfate (HS0 ₄ ), and potassium sulfate (K ₂ S0 ₄ ). A ratio of 3: 2 is obtained by mixing. This etchant removes portions of the indium oxide layer that need to be removed without damaging the photoresist pattern or the underlying layers of the indium oxide layer.

在日本佳能公司专利申请公开的 JP20060209859中，采用乙酸、柠檬酸、盐酸或高氯酸对含有铟和镓或锌的非晶氧化物层进行蚀刻。 In JP20060209859, which is disclosed in Japanese Patent Application, the amorphous oxide layer containing indium and gallium or zinc is etched using acetic acid, citric acid, hydrochloric acid or perchloric acid.

在日本三菱公司专利申请公开的 JP20060145440中，采用一种新颖性的蚀刻组合物包括有机羧酸化合物，乙酸，丙酸，丁酸，琥珀酸，柠檬酸，乳酸，苹果酸，酒石酸，丙二酸，马来酸，戊二酸，乌头酸， 1， 2， 3-丙烷三羧酸，或它们的铵盐聚磺酸化合物和水用在以氧化锌为主要成分，包括铝和 /或镓的导电膜的刻蚀上。 A novel etching composition comprising an organic carboxylic acid compound, acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, is disclosed in JP20060145440, which is hereby incorporated by reference. , maleic acid, glutaric acid, aconitic acid, 1, 2, 3-propane tricarboxylic acid, or their ammonium salt polysulfonic acid compound and water used in zinc oxide as a main component, including aluminum and/or gallium The etching of the conductive film.

在日本佳能公司专利申请公开的 JP20060328204中，采用含有氨的质量浓度在 4. 6%到 28%的碱性溶液对含镓、锌和铟的非晶氧化物半导体膜进行选择性蚀刻。 In JP20060328204 published by the Japanese Canon Patent Application, the quality of ammonia is used. The amorphous oxide semiconductor film containing gallium, zinc and indium is selectively etched in an alkaline solution of 4.6% to 28%.

蚀刻铟氧化物层的常规蚀刻剂包括韩国专利公开第 96-2903号中提及的王水基蚀刻剂 (HC1+HN0₃)，韩国专利公开第 97- 65685号中提及的包含盐酸、弱酸和醇基化合物之一的蚀刻剂，美国专利第 5456795号中提及的三氯化铁基蚀刻剂 (FeCl₃)，韩国专利公开第 2000-0017470中提及的包含草酸、草酸盐和氯化铝作为主要成分的蚀刻剂，以及美国专利第 5340491号中提及的包含碘化氢 (HI) 和氯化铁 (FeCl₃)的蚀刻剂。 A conventional etchant for etching an indium oxide layer includes a water-based etchant (HC1 + HNO ₃ ) mentioned in Korean Patent Publication No. 96-2903, and a hydrochloric acid, a weak acid, and an alcohol are mentioned in Korean Patent Publication No. 97-65685. An etchant for one of the base compounds, an iron trichloride-based etchant (FeCl ₃ ) as mentioned in U.S. Patent No. 5,456,795, and oxalic acid, oxalate and aluminum chloride as mentioned in Korean Patent Publication No. 2000-0017470 An etchant as a main component, and an etchant containing hydrogen iodide (HI) and ferric chloride (FeCl ₃ ) as mentioned in U.S. Patent No. 5,344,491.

在日本卡西欧公司专利申请公开的 JP2006080172A中，为使蚀刻液的氧化锌 (ZnO) 相对容易集中控制，专利将异丙醇（IPA)添加到水中磷酸用于锌氧化膜的蚀刻。 In JP2006080172A, which is disclosed in Japanese Patent Application Laid-Open, the zinc oxide (ZnO) of the etching liquid is relatively easy to be collectively controlled. The patent adds isopropyl alcohol (IPA) to phosphoric acid in water for etching of the zinc oxide film.

在上述披露的各种氧化物蚀刻液和蚀刻方法中，大多集中在研究各种蚀刻液对刻蚀速率的影响，比如通过控制浓度、刻蚀时间、蚀刻组合等方式来调节刻蚀速率，但存在如下问题： In the various oxide etching solutions and etching methods disclosed above, most of them focus on the effects of various etching solutions on the etching rate, such as adjusting the etching rate by controlling the concentration, etching time, etching combination, etc., but There are the following problems:

现已公开的氧化锌和其合金材料的湿法刻蚀方法主要集中在盐酸（HC1 )、磷酸 ( )、醋酸（HAc)、氯化铵（腿 ₄C1 )、三氯化铁 (FeCls)等各种酸溶液和酸式盐溶液。在使用上述酸溶液作为刻蚀剂时，常会出现刻蚀速率不均匀的现象造成刻蚀后样品表面粗糙，并且刻蚀速率也不易控制；在使用丽 ₄C1作为刻蚀剂时会对材料的光电特性造成很大影响并且刻蚀表面粗糙；在使用 FeCl₃溶液作为刻蚀剂时，刻蚀后表面残留的 Fe³⁺很难清洗干净。 The wet etching methods of zinc oxide and its alloy materials which have been disclosed are mainly concentrated in hydrochloric acid (HC1), phosphoric acid (), acetic acid (HAc), ammonium chloride (leg ₄ C1 ), ferric chloride (FeCls), etc. Various acid solutions and acid salt solutions. When the above acid solution is used as an etchant, the etching rate is uneven, and the surface of the sample after etching is rough, and the etching rate is not easy to control. When using Li ₄ C1 as an etchant, the material will be The photoelectric characteristics have a great influence and the etching surface is rough; when FeCl ₃ solution is used as an etchant, the residual Fe ^{3+ on the} surface after etching is difficult to clean.

文献 Semicond. Sci. Technol. 17 (2002) 510提到了，在使用上述酸作为刻蚀液时，常会出现刻蚀速率不均匀的现象，通常表现为刻蚀面呈型的剖面形貌，这种形貌对于半导体器件的质量具有致命的影响。例如，制作最为常用的 pn结时，如果刻蚀中出现 " W"形剖面，会使器件 p区与 n区之间断路，从而直接导致器件制作的失败。在披露的文献中， E Harush在氮化镓材料的电化学刻蚀实验中，建立了理论模型，并声称该模型适用于所有的 "质量转移体系" 即所有的刻蚀体系。文献中提到通过提高腐蚀剂的浓度，从而提高刻蚀速率来解决" W"型剖面的问题，但是高速刻蚀带来的刻蚀过程不好控制的问题同样十分严重。 The literature Semicond. Sci. Technol. 17 (2002) 510 mentions that when the above acid is used as the etching solution, the etching rate is often uneven, which is usually characterized by the profile of the etched surface. Morphology has a fatal impact on the quality of semiconductor devices. For example, when making the most commonly used pn junction, if a "W" shaped cross section occurs in the etch, the device p region and the n region are broken, which directly leads to device fabrication failure. In the published literature, E Harush established a theoretical model for the electrochemical etching experiment of gallium nitride materials and claimed that the model is applicable to all "mass transfer systems", ie all etch systems. It is mentioned in the literature that the problem of "W" profile is solved by increasing the concentration of the etchant and thereby increasing the etching rate, but the problem of poor control of the etching process by high-speed etching is also very serious.

另外，现有技术中大多数已知的蚀刻剂都具有较高的化学活性，它们会腐蚀由耐化学性较差的金属如 Mo、 Al、 Cr制成的邻近层。因此，具有多层结构的电子器件如 IGZ0薄膜晶体管液晶显示器（TFT- LCD) 对多层结构的组成有限制。 In addition, most of the known etchants in the prior art have high chemical activity, which can erode adjacent layers made of less chemically resistant metals such as Mo, Al, Cr. Therefore, an electronic device having a multilayer structure such as an IGZ0 thin film transistor liquid crystal display (TFT-LCD) has a limited composition of a multilayer structure.

更为关键的是，使用上述刻蚀液极容易造成蚀刻面的侧蚀现象，这是由于无论是弱酸还是强酸溶液，都是为液态溶液蚀刻材料，不可避免的具有 H+释放过快、具有低的表面张力和升温易挥发造成蚀刻浓度变化的特点，使得刻蚀向纵深方向发展，导致刻蚀工艺中存在可控性不高、侧蚀严重、产品蚀刻损伤、影响产品特性、降低产品良率等现象。技术问题 More critically, the use of the above etching solution is very likely to cause side etching of the etched surface, which is due to Whether it is a weak acid or a strong acid solution, it is an etching material for a liquid solution. It is inevitable that H+ is released too fast, has a low surface tension, and is heated and volatile to cause a change in etching concentration, so that etching progresses in the depth direction, resulting in engraving. In the etching process, there are phenomena such as low controllability, severe side etching, product etching damage, affecting product characteristics, and reducing product yield. technical problem

为克服上述技术缺陷，本发明公开了一种用于氧化物材料体系的可抑制侧蚀、防止刻蚀不均以及防止刻蚀残留问题的新型蚀刻液。技术解决方案 In order to overcome the above technical drawbacks, the present invention discloses a novel etching liquid for an oxide material system which can suppress side etching, prevent etching unevenness, and prevent etching residue. Technical solution

本发明公开的一种用于氧化物材料体系的新型蚀刻液，包括氧化物蚀刻溶液、起到稠度调节作用的调节剂以及水。 A novel etching solution for an oxide material system disclosed in the present invention includes an oxide etching solution, a regulator for consistency adjustment, and water.

以重量计，所述新型蚀刻液中含有， The new etching solution contains, by weight,

0. 01〜80wt %的氧化物蚀刻溶液； 0. 01~80wt% of an oxide etching solution;

0. l〜80wt %的调节剂； 0. l~80wt% of the modifier;

余量的水。 The balance of water.

所述氧化物材料体系为由锌、铟、镓、铝、锡、镉、铜、锶、钛金属元素构成的二元材料体系、三元材料体系、四元材料体系、多元材料体系、掺杂氧化物材料体系以及由上述材料体系中的两种或两种以上构成的复合材料体系。 The oxide material system is a binary material system composed of zinc, indium, gallium, aluminum, tin, cadmium, copper, bismuth, titanium metal elements, a ternary material system, a quaternary material system, a multi-material system, doping An oxide material system and a composite system composed of two or more of the above material systems.

其中，所述二元材料体系的化学式可表示为 A_x0_y，其中 x>0、 y〉0， A为上述各种金属元素中任意一种， 0为氧元素，其中典型的材料为氧化锌（Zn0)、氧化锡（Sn0₂)、氧化镓（G¾0₃)、氧化铟（In₂0₃)、氧化镉 (CdO) 等； Wherein, the chemical formula of the binary material system can be expressed as A _x 0 _y , wherein x>0, y>0, A is any one of the above various metal elements, and 0 is an oxygen element, wherein a typical material is oxidation. zinc (Zn0), a tin oxide (Sn0 _2), gallium oxide (G¾0 _3), indium oxide (In ₂ 0 _3), cadmium oxide (CdO) and the like;

其中，所述三元材料体系的化学式可表示为 A_XBA, 其中 x〉0、 y〉0、 z>0, A 和 B分别为上述各种金属元素中任意一种， 0为氧元素，其中典型的材料为钛酸锶（SrTi0₃)、锡酸镉（Cd₂Sn0₄)、铟酸镉 (Cd₂In0₄) 等； Wherein, the chemical formula of the ternary material system can be expressed as A _X BA, wherein x>0, y>0, z>0, A and B are respectively any one of the above various metal elements, and 0 is an oxygen element. Typical materials are barium titanate (SrTi0 ₃ ), cadmium stannate (Cd ₂ Sn0 ₄ ), cadmium indium (Cd ₂ In0 ₄ ), etc.

其中，所述四元材料体系的化学式可表示为 A_xB_y O_ffl，其中 x〉0、 y〉0、 z>0、 m>0, A、 B和 C分别为上述各种金属元素中任意一种， 0为氧元素，其中典型的材料为铟镓锌氧化合物（InGaZnO, 简称为 IGZ0) 等。 Wherein, the chemical formula of the quaternary material system can be expressed as A _x B _y O _ffl , where x>0, y>0, z>0, m>0, and A, B and C are respectively among the above various metal elements. Any one, 0 is an oxygen element, and a typical material is indium gallium zinc oxide (InGaZnO, abbreviated as IGZ0).

其中，所述多元材料体系为含有四种以上上述提到的金属元素的氧化物；其中，所述掺杂氧化物材料体系主要是在上述二元、三元、四元或多元材料体系中掺入硼（B)、铝（Al )、镓（Ga)、铟（In) 和锶（Sc) 等第 III族元素，或掺入硅 (Si ),锗（Ge)、锡 (Sn)、铅（Pb)、钛（Ti )、镐 (Zr)和铪 (Hf) 等第 IV族元素，或掺入氟（F)、氯（C1 )等第七主族元素，或掺入稀土元素如锶（Sr)或钇（Y)，也可掺入 F—替代上述材料中 0 其中典型的材料为 In₂0₃:Sn (简称为 IT0)、 ΖηΟ: Ιη (简称为 IZ0或 ΖΙ0)、 Ζη0:Α1 (简称为 ΑΖ0或 ZA0)、 ZnO:Ga (简称为 GZO或 ZG0)、 Sn0₂:Sb (简称为 AT0)、 Sn0₂:F (简称为 FT0)、 ZnO:F、 ZnO:B、 In₂0₃:Ga、 In₂0₃:Al、 ZnO: Sn、 Sn0₂:Al、 Sn0₂:Ga、 Sn0₂: ln等; 所述氧化物蚀刻溶液为无机酸溶液及其酸式盐溶液、有机酸溶液及其铵盐聚磺酸化合物和水碱溶液、碱溶液、盐溶液、双氧水（ 0₂)溶液，以及将上述氧化物蚀刻溶液任意混合而不会产生新的物质而构成的组合蚀刻液。 Wherein the multi-material system is an oxide containing four or more of the above-mentioned metal elements; wherein the doped oxide material system is mainly doped in the above binary, ternary, quaternary or multi-material system Group III elements such as boron (B), aluminum (Al), gallium (Ga), indium (In), and antimony (Sc), or doped with silicon (Si), germanium (Ge), tin (Sn), lead Group IV elements such as (Pb), titanium (Ti), lanthanum (Zr), and hafnium (Hf), or doped with a seventh main group element such as fluorine (F) or chlorine (C1), or doped with a rare earth element such as lanthanum (Sr) or 钇 (Y), may also be incorporated with F—instead of 0 of the above materials, wherein the typical materials are In ₂ 0 ₃ :Sn (abbreviated as IT0), ΖηΟ: Ιη (referred to as IZ0 or ΖΙ0), Ζη0: Α1 (referred to as ΑΖ0 or ZA0), ZnO: Ga (abbreviated as GZO or ZG0), Sn0 ₂ : Sb (abbreviated as AT0), Sn0 ₂ : F (abbreviated as FT0), ZnO: F, ZnO: B, In ₂ 0 ₃ : Ga, In ₂ 0 ₃ : Al, ZnO: Sn, Sn0 ₂ : Al, Sn0 ₂ : Ga, Sn0 ₂ : ln, etc.; the oxide etching solution is a mineral acid solution and an acid salt solution thereof, an organic acid solution and an ammonium salt polysulfonic acid thereof The compound and the aqueous alkaline solution, the alkali solution, the salt solution, the hydrogen peroxide (0 ₂ ) solution, and the combined etching solution which is formed by mixing the above oxide etching solution arbitrarily without generating a new substance.

需要提出的是，上述氧化物蚀刻溶液中列出的蚀刻液大部分是在已有的专利技术中公开的用在氧化物蚀刻中，发明人也知道，上述氧化物蚀刻溶液中提到的组分也是不能任意组合成蚀刻液的，比如酸溶液和碱溶液混合是会产生其它新的生成物，这种混合后会产生新的生成物的组合蚀刻液不应包括在本发明中的氧化物蚀刻溶液范围中。 It is to be noted that most of the etching solutions listed in the above oxide etching solutions are used in oxide etching as disclosed in the prior art, and the inventors also know that the groups mentioned in the above oxide etching solutions are mentioned. The fractions cannot be arbitrarily combined into an etchant. For example, mixing of an acid solution and an alkali solution produces other new products, and the combined etchant which produces a new product after such mixing should not include the oxide in the present invention. In the range of etching solutions.

我们应当指出，上述氧化物蚀刻溶液提到的多数组分经过任意混合后，不会产生新的生成物，也即意思是不产生新的化学生成物，这种混合后不产生新的生成物的组合蚀刻液是包括本发明的中氧化物蚀刻溶液范围中。比如酸溶液和酸式盐溶液构成的组合蚀刻液、碱溶液和碱式盐溶液构成的组合蚀刻液、不同种酸溶液混合构成的组合蚀刻液、不同种碱溶液混合构成的组合蚀刻液等，典型的有使用盐酸（HC1 ) 溶液或者磷酸（¾P0₄) 与醋酸（C¾C00H) 的混合液构成的蚀刻液等，不再一一举例。 It should be pointed out that most of the components mentioned in the above oxide etching solution do not produce new products after arbitrarily mixing, that is, no new chemical products are produced, and no new products are produced after such mixing. The combined etchant is included in the range of intermediate oxide etching solutions of the present invention. For example, a combined etching solution composed of an acid solution and an acid salt solution, a combined etching solution composed of an alkali solution and a basic salt solution, a combined etching liquid composed of a mixture of different kinds of acid solutions, and a combined etching liquid composed of a mixture of different kinds of alkali solutions, Typical examples include an etching solution using a hydrochloric acid (HC1) solution or a mixture of phosphoric acid (3⁄4P0 ₄ ) and acetic acid (C3⁄4C00H), and the like.

本发明中的组合蚀刻液还包括异丙醇（IPA)添加到磷酸溶液中形成的组合蚀刻液。 The combined etching solution of the present invention further comprises a combined etching solution formed by adding isopropyl alcohol (IPA) to a phosphoric acid solution.

在本发明中，所述无机酸溶液为王水、硫酸、盐酸、硝酸、氢碘酸、高氯酸、磷酸、草酸、醋酸、碳酸、氢硫酸、硼酸；所述有机酸溶液为有机羧酸化合物、乙酸、丙酸、丁酸、琥珀酸、柠檬酸、乳酸、苹果酸、酒石酸、丙二酸、马来酸、戊二酸、乌头酸、 1， 2, 3-丙垸三羧酸，或它们的铵盐聚磺酸化合物和水碱溶液；所述碱溶液为氨水；所述盐溶液为上述无机酸、有机酸和碱溶液形成的各种盐溶液，优选为如硫酸氨、硝酸氨或磷酸氨、氯化物弱酸盐、四甲基氢氧化铵 (TMAH)、磷酸盐类化合物、草酸类化合物、氯化铁（FeCl₃)、氯化铵、三氯化铁中任意一种或几种。 In the present invention, the inorganic acid solution is aqua regia, sulfuric acid, hydrochloric acid, nitric acid, hydroiodic acid, perchloric acid, phosphoric acid, oxalic acid, acetic acid, carbonic acid, hydrosulfuric acid, boric acid; the organic acid solution is an organic carboxylic acid Compound, acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, maleic acid, glutaric acid, aconitic acid, 1, 2, 3-propentricarboxylic acid Or an ammonium salt polysulfonic acid compound and an aqueous alkali solution; the alkali solution is ammonia water; the salt solution is a salt solution formed by the above inorganic acid, organic acid and alkali solution, preferably such as ammonium sulfate, nitric acid Any one of ammonia or ammonium phosphate, chloride weak acid salt, tetramethylammonium hydroxide (TMAH), phosphate compound, oxalic acid compound, ferric chloride (FeCl ₃ ), ammonium chloride, and ferric chloride Or several.

所述调节剂选择聚乙二醇、甲氧基聚乙二醇、聚丙二醇、聚乙烯醇、胶体二氧化硅、羚甲基纤维素（CMC)、羚甲基纤维素钠（CMC- NA)、水凝胶、海藻酸钠、液状石蜡、凡士林、植物油一种或几种。 The regulator is selected from the group consisting of polyethylene glycol, methoxy polyethylene glycol, polypropylene glycol, polyvinyl alcohol, colloidal silica, antelope methyl cellulose (CMC), and antelope methyl cellulose sodium (CMC-NA). , hydrogel, sodium alginate, liquid paraffin, petrolatum, vegetable oil one or several.

上面提到的典型的调节剂有聚乙二醇，其结构式为 H0CH₂ (C¾0CH₂) _nC¾0H或 H (0C¾CH₂)„0H, 是平均分子量 200-8000或 8000以上的乙二醇高聚物的总称。随着平均分子量的不同，性质也产生差异，从无色无臭粘稠液体至蜡状固体，毒性随分子量的增加而减少，分子量 4000- 8000的聚乙二醇对人体安全。上面提到的典型的调节剂材料有聚丙二醇，其结构式为 (C₃ 0) _n，其平均分子量一般在 400〜2050之间，无色到淡黄色的粘性液体，较低分子量聚合物能溶于水形成粘稠状液体。 The typical regulator mentioned above is polyethylene glycol, which has the formula H0CH ₂ (C3⁄40CH ₂ ) _n C3⁄40H or H (0C3⁄4CH ₂ ) „0H, which is an ethylene glycol high polymer having an average molecular weight of 200-8000 or more. As the average molecular weight varies, the properties also vary. From colorless, odorless viscous liquids to waxy solids, toxicity decreases with increasing molecular weight, and polyethylene glycol with a molecular weight of 4000-8000 is safe for humans. The typical regulator material mentioned above is polypropylene glycol, which has the formula (C ₃ 0) _n , and its average molecular weight is generally between 400 and 2050. It is a colorless to pale yellow viscous liquid, and a lower molecular weight polymer is soluble. Forming a viscous liquid in water.

上面提到的典型的调节剂材料有聚乙烯醇，其结构式为 (C₂H₄0) _n，其分子量依聚合度的不同而变化，可溶于水形成粘稠状液体。 The typical regulator material mentioned above is polyvinyl alcohol, which has the structural formula (C ₂ H ₄ 0) _n , and its molecular weight varies depending on the degree of polymerization, and is soluble in water to form a viscous liquid.

本发明中的调节剂材料在氧化物蚀刻中的作用主要是起到稠度调节剂的作用，这类材料与水以适当比例混合能形成具有一定粘稠状的液体。如上面所述，发明人选取聚乙二醇、聚丙二醇、聚乙烯醇等三种材料举例是为了对适合作为调节剂材料的特征的进一步说明，只要能起到上述稠度调节作用的其他调节剂同样适合作为本发明的调节剂材料。 The modifier material of the present invention acts primarily in the oxide etch to act as a consistency regulator which mixes with water in a suitable ratio to form a liquid having a viscous appearance. As described above, the inventors selected three materials such as polyethylene glycol, polypropylene glycol, and polyvinyl alcohol as examples for further explanation of characteristics suitable as a regulator material, as long as it can serve as a regulator for the above-mentioned consistency adjustment. It is also suitable as a regulator material of the present invention.

所述水为去离子水。 The water is deionized water.

所述新型蚀刻液的黏度值为 3〜50000 mPa S (这里的数值为 20°C环境测得），其粘稠度可根据氧化物蚀刻溶液、调节剂和水的配比不同而变化。 The viscosity of the novel etching solution is 3 to 50000 mPa S (the value here is measured at 20 ° C environment), and the viscosity thereof may vary depending on the ratio of the oxide etching solution, the regulator, and the water.

进一步地，以重量计，所述新型蚀刻液中含有， Further, the novel etching solution contains, by weight,

0. 01〜80wt %的磷酸或磷酸盐溶液； 0. 01~80wt% phosphoric acid or phosphate solution;

0. l〜80wt %的聚乙二醇调节剂； 0. l~80wt% of a polyethylene glycol regulator;

余量的水。 The balance of water.

对本发明的新型蚀刻液，可由质谱分析（MS)、红外光谱分析（IR)和能谱分析（EDS)等测试手段对该蚀刻液中进行成分介定，尤其是对调节剂特征的功能基团判定。 For the novel etching solution of the present invention, the composition of the etching solution can be determined by means of mass spectrometry (MS), infrared spectroscopy (IR) and energy spectrum analysis (EDS), especially functional groups characteristic of the regulator. determination.

具体而言： in particular:

对于由聚乙二醇作为调节剂构成的蚀刻液，其成分判定方式为采用质谱分析（MS)确定溶液中 CH₂C¾0基团的存在； For an etching solution composed of polyethylene glycol as a regulator, the composition is determined by mass spectrometry (MS) to determine the presence of a CH ₂ C 3⁄40 group in the solution;

对于由聚丙二醇作为调节剂构成的蚀刻液，其成分判定方式为采用质谱分析（MS)确定溶液中 C₃¾0基团的存在。 For an etchant composed of polypropylene glycol as a regulator, the composition is determined by mass spectrometry (MS) to determine the presence of a C ₃ 3⁄40 group in the solution.

为提高蚀刻性能，本发明新型蚀刻液还可以包含己知添加剂。添加剂的种类可以包括但不限于表面活性剂、金属离子鳌合剂以及腐蚀抑制剂。可向蚀刻剂中加入表面活性剂以通过降低表面张力确保蚀刻的均匀性。优选使用能经受蚀刻剂且能与蚀刻剂相容的表面活性剂。例如，本发明中可使用阴离子表面活性剂、阳离子表面活性剂、两性表面活性剂以及非离子表面活性剂。还可以向蚀刻剂中加入氟基表面活性剂。此外，还可以加入现有技术中己知的多种添加剂。 In order to improve the etching performance, the novel etching solution of the present invention may further contain a known additive. Types of additives can include, but are not limited to, surfactants, metal ion chelators, and corrosion inhibitors. A surfactant may be added to the etchant to ensure uniformity of etching by reducing surface tension. It is preferred to use a surfactant which is capable of withstanding an etchant and which is compatible with an etchant. For example, an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used in the present invention. It is also possible to add a fluorine-based surfactant to the etchant. In addition, various additives known in the art can be added.

添加剂的加入范围为蚀刻剂总重量的约 0. 0001wt%〜约 10wt %。 The additive is added in an amount ranging from about 0.0001 wt% to about 10 wt%, based on the total weight of the etchant.

本发明还公开了上述新型蚀刻液的蚀刻方法，该方法包括如下步骤： (1)在氧化物单层或多层材料体系上喷雾涂布光阻胶形成光阻胶图案；The invention also discloses an etching method for the above novel etching liquid, which method comprises the following steps: (1) spraying a photoresist on a single layer or a multilayer material system to form a photoresist pattern;

(2)将新型刻蚀液通过涂覆方式一次或多次涂覆在具有光阻胶图案的氧化物单层或多层上； (2) applying a new etching solution to the oxide single layer or multiple layers having the photoresist pattern one or more times by coating;

(3)利用新型刻蚀液蚀刻通过光阻胶图案选择性地蚀刻氧化物层。 (3) The oxide layer is selectively etched through the photoresist pattern using a novel etching solution.

所述蚀刻液涂覆可以采用甩胶机、旋涂机、喷雾机来实现，优选方法为甩胶机和喷雾机。 The etchant coating can be carried out using a silicone machine, a spin coater, a sprayer, and the preferred method is a silicone machine and a sprayer.

所述蚀刻液涂覆的厚度在 5〜10000nm。 The etching solution is applied to a thickness of 5 to 10000 nm.

所述蚀刻液涂覆的温度在 0〜200度。 The etching solution is applied at a temperature of 0 to 200 degrees.

所述氧化物单层或多层材料体系为为 ZnO材料体系时，其蚀刻方法具体为：在沉积生长 ZnO基透明导电薄膜的衬底喷雾涂布光阻胶；进行曝光、显影，去除部分光阻胶，使得待刻蚀衬底暴露在外；对其进行烘烤；通过对待蚀刻衬底喷雾涂布上新型蚀刻液；刻蚀时间范围 0. 5分钟到 30分钟，蚀刻温度不高于 150摄氏度；去离子水冲洗；有机溶液去除光阻胶；测量刻蚀的侧蚀深度和刻蚀图形形状。 When the oxide single-layer or multi-layer material system is a ZnO material system, the etching method is specifically: spraying a photoresist on a substrate on which a ZnO-based transparent conductive film is deposited and deposited; performing exposure, development, and removing part of the light Resisting the adhesive, exposing the substrate to be etched; baking it; spraying a new etching solution by spraying the substrate to be etched; etching time range of 0.5 minutes to 30 minutes, etching temperature not higher than 150 degrees Celsius ; rinse with deionized water; remove the photoresist from the organic solution; measure the etched depth of the etch and the shape of the etched pattern.

所述 ZnO基透明导电薄膜为 ZnO: Al、 Zn0:Ga、 Zn0: ln、 Zn0:Sn、 InGaZnO中任意一种或几种组合物。 The ZnO-based transparent conductive film is any one or more of ZnO: Al, Zn0: Ga, Zn0: ln, Zn0: Sn, and InGaZnO.

本发明在传统的氧化物蚀刻液中添加适当的调节剂，并且与水通过适当的比例混合，获得了刻蚀 "氧化物材料体系"的 "新型蚀刻液"。本发明的新型蚀刻液与传统蚀刻液比较，其中一个重要区别是传统蚀刻液为水溶液，其典型的黏度（也叫粘度）值为 0. 1〜3 mPa S (黏度值受温度的影响明显，这里的数值为 20°C环境测得，水在该条件下的黏度值为 l. O mPa'S), 而本发明的新型蚀刻液是具有一定粘稠度的胶状溶液，其典型的黏度值为 3〜50000 mPa S (这里的数值为 20°C环境测得），该黏度值可根据传统蚀刻液、调节剂和水的调节比例不同而变化。 The present invention adds a suitable modifier to a conventional oxide etchant and mixes it with water in an appropriate ratio to obtain a "new etchant" for etching an "oxide material system". 1〜3 mPa S (The viscosity value is obviously affected by temperature, the important difference is that the conventional etching liquid is an aqueous solution, and the typical viscosity (also called viscosity) is 0. 1~3 mPa S (the viscosity value is obviously affected by temperature, The value here is measured in an environment of 20 ° C, and the viscosity of water under the condition is 1.0 mPa'S), and the novel etching solution of the present invention is a gel solution having a certain viscosity, and the typical viscosity value thereof is a typical viscosity value. 3~50000 mPa S (the value here is measured at 20 °C environment), the viscosity value can be changed according to the adjustment ratio of the conventional etching solution, the regulator and the water.

发明人发现，本发明的新型蚀刻液的黏度值对于 "氧化物材料体系"的刻蚀效果是有很大影响的。比如传统盐酸水溶液刻蚀 ZnO材料中，主要的刻蚀机理是电离的 H+离子对刻蚀起作用，电离的 H+离子的浓度和活动范围直接影响刻蚀效果。电离的 H⁺离子在黏度值很小的水溶液中有较大的运动范围，而使得刻蚀速率不可控，容易造成 ZnO材料侧蚀、刻蚀不均现象，而本发明的新型蚀刻液具有一定的粘稠度从而能够减小 H+离子的运动范围，控制刻蚀速率，抑制过分刻蚀。 The inventors have found that the viscosity value of the novel etching solution of the present invention has a great influence on the etching effect of the "oxide material system". For example, in the traditional HCl etching of ZnO materials, the main etching mechanism is that ionized H+ ions act on the etching. The concentration and range of ionized H+ ions directly affect the etching effect. The ionized H ⁺ ions have a large range of motion in an aqueous solution having a small viscosity value, so that the etching rate is uncontrollable, which tends to cause side etching and uneven etching of the ZnO material, and the novel etching liquid of the present invention has certain The viscosity thus reduces the range of motion of the H+ ions, controls the etch rate, and suppresses excessive etching.

发明人还发现，在本发明的新型蚀刻液中调节剂对于 "氧化物材料体系" 的刻蚀效果尤其是抑制侧蚀方面是有很大影响的。适合充当稠度调节剂的调节剂，通常由大分子聚合物构成，能够对电离的 H+离子起到限制作用，防止 H+离子顺着 ZnO材料晶界等薄弱处刻蚀，从而抑制侧蚀。有益效果 The inventors have also found that in the novel etchant of the present invention, the modifier has a great influence on the etching effect of the "oxide material system", particularly on the side etching. It is suitable as a regulator of consistency regulators, usually composed of macromolecular polymers, which can limit the ionized H+ ions and prevent H+ separation. The sub-etch is etched along a weak point such as the grain boundary of the ZnO material to suppress side etching. Beneficial effect

采用新型蚀刻液与对比盐酸蚀刻液制作的 ZnO透明电极的基 LED芯片的芯片光电测试结果比对如图 8所示;可见在保证漏电良率相同的工艺制作情况下，有机磷酸胶湿法蚀刻工艺比稀释盐酸湿法蚀刻法具有更高的 ZnO TCL发光面积，其电流扩展面积大，电流密度小，同时金属 PAD接触 TCL的面积也比酸液法的大，新型蚀刻液相比对比盐酸蚀刻液蚀刻工艺可提高 LED亮度和降低工作电压，提高器件的发光效率，采用新型蚀刻液与盐酸蚀刻液制作的 ZnO透明电极的基 LED芯片器件测试结果如表 1所示。 The photodetection results of the chip of the ZnO transparent electrode made by the new etching solution and the comparative hydrochloric acid etching solution are shown in Fig. 8; it can be seen that the organic phosphoric acid gel is wet etched under the same process of ensuring the same leakage yield. The process has a higher ZnO TCL light-emitting area than the diluted hydrochloric acid wet etching method, and has a large current expansion area and a small current density. At the same time, the area of the metal PAD contacting the TCL is larger than that of the acid method, and the new etching liquid is compared with the hydrochloric acid etching. The liquid etching process can improve the brightness of the LED and reduce the working voltage, and improve the luminous efficiency of the device. The test results of the basic LED chip device of the ZnO transparent electrode made by using the new etching liquid and the hydrochloric acid etching liquid are shown in Table 1.

表 1 Table 1

由上可见，本发明的 "涂层"蚀刻方法具有以下优点： As can be seen from the above, the "coating" etching method of the present invention has the following advantages:

(1)对 "涂层"厚度及刻蚀速率的控制。 (1) Control of "coating" thickness and etching rate.

(2)旋涂的方法可使蚀刻液体形成一层薄膜，均匀覆盖在样品上面，流动性少，可确保其蚀刻的区域均匀性； (2) The method of spin coating can form a thin film of the etching liquid, uniformly covering the sample, and having less fluidity, thereby ensuring the uniformity of the etched region;

(3)由于粘稠的蚀刻液体比起湿法浸泡蚀刻的溶液浸润性少，使其侧向侵蚀的状况要好于湿法浸泡法。因此，我们可以通过增加 H+离子浓度和延长蚀刻时间的办法来清楚底部残留。同时此方法还可以应用于单层或多层氧化物薄膜刻蚀的情况； (3) Since the viscous etching liquid has less wettability than the wet immersion etching solution, the lateral erosion condition is better than the wet immersion method. Therefore, we can clear the bottom residue by increasing the H+ ion concentration and extending the etching time. At the same time, the method can also be applied to the case of etching of a single layer or a plurality of oxide films;

(4)本发明的蚀刻液对氧化物薄膜层有良好的蚀刻能力；精确的深度蚀刻和缓慢的蚀刻速率，具有良好的可控性；工艺步骤简单，并相比于其它湿法蚀刻，具有良好的安全性。 (4) The etching liquid of the present invention has good etching ability to the oxide thin film layer; precise deep etching and slow etching rate have good controllability; the process steps are simple, and compared with other wet etching, Good security.

下面再通过对不同的组分和含量的新型蚀刻液的试验效果进行说明。本实施例的新型蚀刻液组成及其实验效果如表 2所示: The test results of the new etching solutions with different compositions and contents will be described below. The composition of the novel etching solution of this embodiment and its experimental effects are shown in Table 2:

表 2不同的新型蚀刻液组成及其效果 Table 2 different new etchant compositions and their effects

氧化物蚀刻液加剂 Oxide etching solution

号调节剂及含量水蚀刻效果 No. Modifier and content water etching effect

及含量 05 添 And content 05

里及含量 And content

硫酸 0. 01wt % 甲氧基聚乙二醇余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec Sulfuric acid 0. 01wt % methoxypolyethylene glycol balance 1 etching AZ0, GZ0, ZnO film: 20sec

1 80wt% 内，侧蚀 <1μπι，侧蚀速率 1 80wt%, side erosion <1μπι, side erosion rate

<3μπι/πιΐη; 刻蚀界面平整，速率可控，表面无残留。 <3μπι/πιΐη; The etching interface is flat, the rate is controllable, and there is no residue on the surface.

盐酸 lwt % 聚乙二醇 75wt% 余量 1 刻蚀 AZ0、 GZ0、 Zn0、 SnU₂ : Ga>Hydrochloric acid lwt % polyethylene glycol 75wt% balance 1 etching AZ0, GZ0, Zn0, SnU ₂ : Ga>

2 In₂0₃ : Sn 薄膜： 20sec 内，侧蚀 2 In ₂ 0 ₃ : Sn film: within 20 sec, side etching

<lum, 侧蚀速率 <3μηι/πΰη; 刻蚀界平整，速率可控，表面无残留。硝酸 10wt% 海藻酸钠 70wt% 余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec <lum, side etching rate <3μηι/πΰη; The etching boundary is flat, the rate is controllable, and there is no residue on the surface. Nitric acid 10wt% sodium alginate 70wt% balance 1 Etching AZ0, GZ0, ZnO film: 20sec

3 内，侧蚀 <3μπι，侧蚀速率 3 inner, side erosion <3μπι, side erosion rate

<9μπι η; 刻蚀界面平整，速率可控，表面无残留。 <9μπι η; The etching interface is flat, the rate is controllable, and there is no residue on the surface.

乙酸 15wt% 凡士林 65wt% 余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec Acetic acid 15wt% Vaseline 65wt% balance 1 Etching AZ0, GZ0, ZnO film: 20sec

4 内，侧蚀 <0. 5um，侧蚀速率 4, side erosion <0. 5um, side erosion rate

<1. 5μπι/ιηίη; 亥 ij蚀界面平整，速率可控，表面无残留。 <1. 5μπι/ιηίη; Hai ij eclipse interface is flat, the rate is controllable, and there is no residue on the surface.

丙酸 20wt% 聚乙烯醇 60wt 余量 1 刻蚀 AZ0、 GZ0、 Zn0、 SnU₂ : Ga> Propionic acid 20wt% Polyvinyl alcohol 60wt Balance 1 Etching AZ0, GZ0, Zn0, SnU ₂ : Ga>

In₂0₃ : Sn薄膜： 20sec内，侧蚀In ₂ 0 ₃ : Sn film: within 20 sec, side etching

5 <0. 5μιιι, 侧蚀速率 <1. 5μπι/πιίη; 5 <0. 5μιιι, etch rate <1. 5μπι/πιίη;

刻蚀界面平整，速率可控，表面无残留。 The etching interface is flat, the rate is controllable, and there is no residue on the surface.

乳酸 25wt% 余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec Lactic acid 25wt% balance 1 Etching AZ0, GZ0, ZnO film: 20sec

6 55wt " 内，侧蚀〈0. 3um，侧蚀速率〈0· 9μπι η; 亥 ij蚀界面平整，速率可控，表面无残留。 6 55wt "inside, side erosion <0. 3um, side erosion rate <0· 9μπι η; Hai ij eclipse interface is flat, the rate is controllable, no residue on the surface.

硫酸氨 30wt% 羚甲基纤维素余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec Ammonia Sulfate 30wt% Antelope Methyl Cellulose Balance 1 Etching AZ0, GZ0, ZnO Film: 20sec

7 50 t % 内，侧蚀 <2μπι , 侧蚀速率 7 50 t % , side erosion <2μπι , side erosion rate

<6um/min_; 刻蚀界面平整，速率可控，表面无残留。 <6um/min _{; the} etching interface is flat, the rate is controllable, and there is no residue on the surface.

磷酸氨 35wt % 水凝胶 45wt% 余量 1 亥 IJ蚀 AZ0、 GZ0、 Zn0、 SnU₂: (ia、 Ammonia phosphate 35wt% hydrogel 45wt% balance 1 Hai IJ etch AZ0, GZ0, Zn0, SnU ₂ : (ia,

In 薄膜： 20sec 内，侧蚀 In film: within 20sec, side etching

8 ₂0₃: Sn 8 ₂ 0 ₃ : Sn

<2μιη，侧蚀速率 <6μιη/πάη; 亥【J蚀界面平整，速率可控，表面无残留。氨水 40wt% 凡士林 40wt% 余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec <2μιη, side etch rate <6μιη/πάη; Hai [J eclipse is flat, the rate is controllable, and there is no residue on the surface. Ammonia water 40wt% Vaseline 40wt% balance 1 Etching AZ0, GZ0, ZnO film: 20sec

9 内，侧蚀 <1μπι，侧蚀速率 9 inside, side erosion <1μπι, side erosion rate

<3μπι/ιηϊη; 刻蚀界面平整，速率可控，表面无残留。 <3μπι/ιηϊη; The etching interface is flat, the rate is controllable, and there is no residue on the surface.

磷酸 10wt % 液状石蜡 35wt% 余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec0 内，侧蚀 <3μπι，侧蚀速率 Phosphoric acid 10wt% liquid paraffin 35wt% balance 1 etching AZ0, GZ0, ZnO film: 20sec0, side etching <3μπι, side etching rate

Ομιπ/πιΐη; 刻蚀界面平整，速率可控，表面无残留。 Ομιπ/πιΐη; The etching interface is flat, the rate is controllable, and there is no residue on the surface.

磷酸盐 50wt % 植物油 30wt% 余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec 1 内，侧蚀〈1μπι，侧蚀速率 Phosphate 50wt% vegetable oil 30wt% balance 1 etching AZ0, GZ0, ZnO film: 20sec 1 , side etching <1μπι, side etching rate

<3μπι η; 刻蚀界面平整，速率可控，表面无残留。 <3μπι η; The etching interface is flat, the rate is controllable, and there is no residue on the surface.

盐酸盐 55wt% 胶体二氧化硅余量 1 刻蚀 AZ0、 GZ0、 Zn0、 SnU₂ : Ga2 25 t % In₂0₃ : Sn 薄膜： 20sec 内，侧蚀 Hydrochloride 55wt% Colloidal silica balance 1 Etching AZ0, GZ0, Zn0, SnU ₂ : Ga2 25 t % In ₂ 0 ₃ : Sn Film: 20sec, side etching

<lum, 侧蚀速率〈3μπι/ιηϋη; 刻蚀界平整，速率可控，表面无残留。硝酸盐 60wt% 聚乙二醇 20wt% 余量 1 刻蚀 AZ0、 GZ0、 ZnO薄膜： 20sec3 内，侧蚀〈1μπι，侧蚀速率 <lum, side erosion rate <3μπι/ιηϋη; The etching boundary is flat, the rate is controllable, and there is no residue on the surface. Nitrate 60wt% Polyethylene glycol 20wt% Balance 1 Etching AZ0, GZ0, ZnO film: 20sec3, side etching <1μπι, side etching rate

<3μηι/πιΐη; 刻蚀界面平整，速率可控，表面无残留。

<3μηι/πιΐη; The etching interface is flat, the rate is controllable, and there is no residue on the surface.

分别对表 2中的列举的新型蚀刻液对氧化物材料体系进行蚀刻，其蚀刻效果具体如表 2所述，均具有良好的蚀刻效果，可以精确控制蚀刻深度、具有平整的刻蚀界面以及可以抑制侧蚀等技术效果。附图说明 The oxide liquid system is etched by the new etching liquids listed in Table 2, and the etching effect is as described in Table 2, which has good etching effect, can accurately control the etching depth, has a flat etching interface, and can It suppresses technical effects such as side erosion. DRAWINGS

图 1是实施例 1中测量的质谱（MS) 数据； Figure 1 is a mass spectrometry (MS) data measured in Example 1;

图 2是实施例 1中的新型蚀刻液和稀盐酸两种刻蚀剂对锌、铟、铝、镓等氧化物材料刻蚀后的 SEM图样； 2 is a novel etching solution and a dilute hydrochloric acid etchant in Example 1 for zinc, indium, aluminum, gallium, etc. SEM pattern after etching of the oxide material;

图 3是实施例 1中的新型蚀刻液对锌、铟、铝、镓等氧化物薄层材料不同时间刻蚀后的刻蚀效果图； 3 is an etching effect diagram of the novel etching solution in Example 1 after etching a thin layer of an oxide such as zinc, indium, aluminum or gallium at different times;

图 4是实施例 1中的示例稀盐酸刻蚀剂对锌、铝、镓等氧化物薄层材料刻蚀后在边缘 ZnO残留层； 4 is an exemplary thin dilute hydrochloric acid etchant in Example 1 after etching a thin layer of an oxide such as zinc, aluminum or gallium;

图 5是实施例 1中的新型蚀刻液对锌、铝、镓等氧化物薄层材料不同时间刻蚀后的侧蚀速率； 5 is a side etching rate of a thin etching material of an oxide liquid such as zinc, aluminum, gallium or the like after etching in a new etching liquid in the first embodiment;

图 6是实施例 1中的新型蚀刻液采用不同的蚀刻方法刻蚀 ZnO: 左图为蚀刻液浸泡反应条件，右图为甩胶机旋涂条件； 6 is a etched etch solution of the novel etchant in the first embodiment using different etching methods: the left picture shows the etching conditions of the etching solution, and the right picture shows the spin coating condition of the squeegee machine;

图 7是实施例 1中的新型蚀刻液在含氧化物材料体系的透明导电薄膜材料蚀刻流程示意； 7 is a flow chart showing the etching process of the transparent conductive film material of the novel etching liquid in the oxide-containing material system in the first embodiment;

图 8是实施例 1中的新型蚀刻液（左）与传统对比 "蚀刻液 A" (右）制作的 ZnO透明电极的基 LED芯片刻蚀后的图样。本发明的最佳实施方式 Fig. 8 is a view showing the etching of the base LED chip of the ZnO transparent electrode produced by the novel etching liquid (left) in the first embodiment and the conventional comparative "etching liquid A" (right). BEST MODE FOR CARRYING OUT THE INVENTION

下面将通过具体实施例对本发明进行详细说明。 The invention will now be described in detail by way of specific examples.

实施例 1: Example 1:

选取由磷酸、聚乙二醇和水调配成新型蚀刻液，其中磷酸浓度优选的为 0. 01〜80wt %，聚乙二醇浓度优选的为 0. l〜80wt %，用于稀释的水含量优选的为 10〜90wt %。各组分不同调配的比例直接影响刻蚀的速率和刻蚀效果，但均具有较好的蚀刻效果，在本实施例中新型蚀刻液由 25%的聚乙二醇、 25%的瞵酸和 50%的水组成，采用质谱分析（MS)、红外光谱分析（IR)和能谱分析（EDS) 等测试手段对该成分进行介定。〜80重量 %的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的优选的It is 10~90wt%. The proportion of different components of each component directly affects the etching rate and etching effect, but both have better etching effect. In this embodiment, the new etching solution consists of 25% polyethylene glycol, 25% tannic acid and The composition of 50% water is determined by means of mass spectrometry (MS), infrared spectroscopy (IR) and energy spectrum analysis (EDS).

通过质谱分析得到待测液的质谱图，如图 1所示，再经质谱仪搜索，与样品所得质谱图所类似物质的成分从相似度从高到底得到的为： C₁₂H₂₄0₆、 C_1QH₂。0₅、 C₁₀H_2OO₅, C₁₂H₂₄0₆、（_1βΗ₂₂0₆。上述结果显示溶液中含有分子式为 H0(CH₂C 0) _nH的聚乙二醇；另外，通过能谱分析（EDS)确定蚀刻液含有的元素种类和含量；通过红外光谱分析（IR) 可以确定溶液中磷酸根的存在。 The mass spectrum of the liquid to be tested is obtained by mass spectrometry. As shown in Fig. 1, after searching by the mass spectrometer, the composition of the substance similar to the mass spectrum obtained from the sample is obtained from the similarity: C ₁₂ H ₂₄ 0 ₆ , C _1Q H ₂ . 0 ₅ , C ₁₀ H _2O O ₅ , C ₁₂ H ₂₄ 0 ₆ , ( _1β Η ₂₂ 0 ₆ . The above results show that the solution contains polyethylene glycol of the formula H0(CH ₂ C 0) _n H ; Energy spectrum analysis (EDS) determines the type and content of elements in the etchant; the presence of phosphate in the solution can be determined by infrared spectroscopy (IR).

因此，对于其它的新型蚀刻液，我们也可以采用上面提到的质谱分析（MS)、红外光谱分析（IR)和能谱分析（EDS)来对溶液成分进行介定，若测得的主要成分属于本发明的新型蚀刻液所披露的材料和特征，也应属于本专利的范畴。 Therefore, for other new etchants, we can also use the mass spectrometry (MS), infrared spectroscopy (IR) and energy spectrum analysis (EDS) mentioned above to mediate the solution components, if the main components are measured. The materials and features disclosed in the novel etching solutions of the present invention are also within the scope of this patent.

下面对本实施例 1中蚀刻液的刻蚀效果来作进一步说明，刻蚀选取的材料为锌、铝、镓等氧化物材料。作为对比，选取稀盐酸作为对比刻蚀液，稀盐酸蚀刻液一般以 lmol/L- 6mol/L为宜，其中 3mol/L的效果最佳。图 2为实施例 1中的新型蚀刻液和稀盐酸蚀刻液蚀刻蚀锌、铝、镓等氧化物材料后的条纹边缘截面图。与稀盐酸刻蚀结果（侧蚀为 5 μ ιη)相比，新型蚀刻液刻蚀条纹的侧蚀小于 l m，边缘过度平滑，腐蚀界面清晰平整，且蚀刻液对锌、铝、镓等氧化物材料带隙间的晶体排列有序。造成两种腐蚀情况不同的原因主要是因为新型蚀刻液中聚乙二醇大分子基团对电离出来的 H+离子活动范围的限制，以及防止 H⁺离子从原子间隙处对材料的深层刻蚀。实验证明新型蚀刻液相对于传统的盐酸蚀刻液，具有蚀刻效果好、精确的厚度蚀刻和可控的侧蚀速率，而且工艺步骤更加简单，具有良好的安全性。 The etching effect of the etching solution in the first embodiment will be further described below. The material selected by etching is an oxide material such as zinc, aluminum or gallium. As a comparison, dilute hydrochloric acid is selected as the contrast etching solution, and the dilute hydrochloric acid etching solution is generally 1 mol/L-6 mol/L, and 3 mol/L is the best. 2 is a cross-sectional view of a stripe edge of a novel etching solution and a dilute hydrochloric acid etching solution in Example 1 after etching an oxide material such as zinc, aluminum or gallium. Compared with the dilute hydrochloric acid etching result (side etch is 5 μ η), the side etching of the etched stripe of the new etching solution is less than lm, the edge is excessively smooth, the etching interface is clear and flat, and the etching solution is oxides of zinc, aluminum, gallium, etc. The crystals between the band gaps of the material are ordered. The reason for the difference between the two types of corrosion is mainly due to the limitation of the range of ionization of the H+ ion in the polyethylene glycol macromolecule in the new etching solution, and the deep etching of the material from the atomic gap by the H ⁺ ion. The experiment proves that the new etching liquid phase has good etching effect, precise thickness etching and controllable side etching rate for the traditional hydrochloric acid etching solution, and the process steps are simpler and have good safety.

更进一步，图 3显示了新型蚀刻液经过多次的对锌、铝、镓等氧化物薄层材料的刻蚀，该氧化物薄层材料上覆盖有一定图形的光阻胶涂层，我们发现经过 1. 5、 3、 6、 12分钟不同时间刻蚀后，氧化物薄层材料依然保持清晰的边界, 侧蚀很小，而且无蚀刻残留，表明新型蚀刻液经过多次的对锌、铟、铝、镓等氧化物材料的刻蚀，显示了很好的刻蚀工艺重复性。 Furthermore, Figure 3 shows the etching of a thin layer of an oxide such as zinc, aluminum or gallium by a new etching solution. The thin layer of the oxide is covered with a certain photoresist coating. After etching at different times for 1.5, 3, 6, and 12 minutes, the oxide thin layer material still maintains a clear boundary, the side etching is small, and there is no etching residue, indicating that the new etching solution passes through the zinc, indium multiple times. The etching of oxide materials such as aluminum and gallium shows a good etching process repeatability.

作为对比，同样比较了不同浓度和时间下的稀盐酸刻蚀液对锌、铟、铝、镓等氧化物薄层材料的刻蚀效果，发觉工艺重复性差。在蚀刻时间为 20s，仍存在较大的侧蚀（>1 μ πι)，并且有样品显示在边缘侧蚀区域有一层很薄的残留，如图 4所示，即传统的刻蚀剂造成的侧蚀、刻蚀不均以及残留问题。 As a comparison, the etching effect of the dilute hydrochloric acid etching solution at different concentrations and times on the thin layer materials of zinc, indium, aluminum, gallium and the like is also compared, and the process repeatability is poor. At the etching time of 20 s, there is still a large side etch (>1 μ πι), and there is a sample showing a very thin residue in the edge etched area, as shown in Figure 4, which is caused by a conventional etchant. Side etching, uneven etching and residual problems.

更进一步，发明人发现，聚乙二醇、磷酸和水组成的新型刻蚀液中，蚀刻速率可以通过调整三者的配比浓度以及温度进行控制，当聚乙二醇占比例大时，新型刻蚀液黏度增大，蚀刻速率降低；同样，蚀刻的速率受到温度的影响，当温度升高时，新型刻蚀液黏度降低，蚀刻速率增大。 Furthermore, the inventors have found that in a new etching solution composed of polyethylene glycol, phosphoric acid and water, the etching rate can be controlled by adjusting the ratio of the three components and the temperature. When the proportion of polyethylene glycol is large, the new type The viscosity of the etching solution is increased and the etching rate is lowered. Similarly, the etching rate is affected by the temperature. When the temperature is raised, the viscosity of the new etching solution is lowered and the etching rate is increased.

图 5显示了新型刻蚀液对锌、铝、镓等氧化物薄层材料不同时间不同温度刻蚀后的侧蚀速率比较图，发明人发现，可以通过调节新型刻蚀液的温度来进一步的抑制侧蚀，另外，当达到较长时间后，侧蚀深度就不再增加了。 Figure 5 shows a comparison of the side etching rates of a new etching solution for a thin layer of zinc, aluminum, gallium and other oxides at different temperatures. The inventors found that the temperature of the new etching solution can be further adjusted. Suppression of side erosion, in addition, after a long time, the depth of the side erosion is no longer increased.

本实施例表明本发明的新型蚀刻液可以解决锌、铟、铝、镓等氧化物薄层材料遇到的侧蚀、刻蚀不均以及残留问题。同样，新型蚀刻液可以从采用的 "聚乙二醇、磷酸和水"组成扩充到本发明提到的整个新型蚀刻液范围，适用的锌、铝、镓等氧化物薄层材料也可扩充到整个氧化物材料体系，其原理是一样的。本发明的实施方式 This embodiment shows that the novel etching solution of the present invention can solve the side etching, uneven etching and residual problems encountered in thin oxide materials such as zinc, indium, aluminum, gallium and the like. Similarly, the new etching solution can be extended from the "polyethylene glycol, phosphoric acid and water" to the entire range of new etching solutions mentioned in the present invention. The applicable thin layer materials such as zinc, aluminum and gallium can also be expanded to The principle of the entire oxide material system is the same. Embodiments of the invention

实施例 2: Example 2:

传统的蚀刻液为溶液状，在刻蚀氧化物材料时，是将氧化物材料浸在溶液中反应，这里称为 "浸泡"刻蚀方式；而对于本发明胶状的新型刻蚀液，可以采用旋涂或者喷雾的方式对氧化物材料进行刻蚀，这里将旋涂或者喷涂方式称为 "涂层"蚀刻方式。 The conventional etching solution is in the form of a solution. When the oxide material is etched, the oxide material is immersed in a solution, which is referred to as a "soaking" etching method; and for the gelatinous novel etching liquid of the present invention, The oxide material is etched by spin coating or spraying, where the spin coating or spraying method is referred to as a "coating" etching method.

本发明的 "涂层"蚀刻方式，其工艺为通过旋涂或者喷涂方式将新型刻蚀液涂覆在具有利用光阻胶形成光阻胶图案的氧化物薄膜材料上，新型刻蚀液涂层对露出的氧化物薄膜材料进行蚀刻，蚀刻结束后，再用去离子水去除残留蚀刻液，可重复利用涂层刻蚀。 The "coating" etching method of the present invention is a method of applying a new etching liquid to an oxide film material having a photoresist pattern formed by using a photoresist by spin coating or spraying, and a novel etching liquid coating. The exposed oxide film material is etched, and after the etching is completed, the residual etching liquid is removed by using deionized water, and the coating etching can be repeated.

本发明在这里采用的 "涂层"蚀刻方式，可以采用通用的旋涂或喷涂设备来实现，比如甩胶机、旋涂机、喷雾机等，本发明中的优选方法为甩胶机和喷雾机。 The "coating" etching method used in the present invention can be realized by a general spin coating or spraying equipment, such as a rubberizing machine, a spin coating machine, a sprayer, etc., and the preferred method in the present invention is a silicone coating machine and a spray. machine.

本实施例的实验样品为用 M0CVD方法在蓝宝石衬底上生长的 250nm的 ZnO 薄膜。经过涂胶、甩胶、烘烤、曝光、显影、后烘烤等步骤形成刻蚀所需条纹图案，暴露 ZnO层。 The experimental sample of this example was a 250 nm ZnO thin film grown on a sapphire substrate by the M0CVD method. The stripe pattern required for etching is formed by a step of coating, sizing, baking, exposing, developing, post-baking, etc., and the ZnO layer is exposed.

控制反应条件为浸泡在蚀刻液内和用甩胶机旋涂的方法。分别对 ZnO样品刻蚀 90s。刻蚀完成后用去离子水洗净，并吹干。然后用显微镜、观察刻蚀后的图案及侧面，并用台阶仪测量刻蚀深度。图 6给出了两种不同涂抹方式下蚀刻液 90s蚀刻 ZnO的电子显微镜图。在浸泡条件下，反应完毕后，发现外延片表面粗糙不平， ZnO沟道上有气泡残留。初步判断为已经反应露出衬底，但有蚀刻液黏附在光阻胶上不易清洗，测量平均侧蚀较大，测试边缘不齐整；在甩胶机旋涂方式下，反应完毕后，掩膜表面图形完整，边缘部分齐整，台阶仪测试沟道 ZnO反应到底，露出衬底。通过实验证明，甩胶机甩胶涂液法相对于浸泡方法较为稳定。 The reaction conditions were controlled by soaking in an etching solution and spin coating with a silicone machine. The ZnO samples were etched for 90 s. After the etching is completed, it is washed with deionized water and blown dry. Then, the etched pattern and the side surface were observed with a microscope, and the etching depth was measured with a step meter. Figure 6 shows an electron micrograph of etched ZnO with 90s etching in two different application methods. Under the immersion conditions, after the reaction was completed, it was found that the surface of the epitaxial wafer was rough and uneven, and bubbles remained on the ZnO channel. It is preliminarily judged that the substrate has been exposed, but the etching solution adheres to the photoresist, which is difficult to clean. The average side corrosion is measured and the test edge is not uniform. In the spin coating mode, after the reaction is completed, the mask surface is completed. The pattern is complete, the edges are neat, and the step meter tests the channel ZnO to the end, exposing the substrate. It has been proved by experiments that the silicone coating method is more stable than the dip coating method.

下面对本发明的蚀刻方法进详细说明，具体如图 7蚀刻流程示意图。 The etching method of the present invention will be described in detail below, specifically as shown in the etching process diagram of FIG.

采用具有 ZnO:Al、 ZnO:Ga、 ZnO: In、 ZnO:Sn、 InGaZnO中任意一种或几种组合物作为透明电极的 LED器件来作说明，选用的蚀刻液为实施例 1中的蚀刻液。 An LED device having any one or more of ZnO:Al, ZnO:Ga, ZnO:In, ZnO:Sn, InGaZnO as a transparent electrode is used for description, and the etching liquid selected is the etching liquid in Embodiment 1. .

首先，利用 M0CVD方法生长的掺 A1的 ZnO基透明导电膜 300nm，对其进行涂胶，甩胶。利用具有图形的光阻胶对掺 A1的 ZnO透明导电膜进行光刻，显影，去掉不需要的光阻胶，获得所需要蚀刻的芯片图形结构。 First, an Al-doped ZnO-based transparent conductive film grown by M0CVD method was coated with 300 nm, and it was subjected to gluing. The Al-doped ZnO transparent conductive film is photolithographically developed by using a patterned photoresist, and the unnecessary photoresist is removed to obtain a chip pattern structure to be etched.

然后，将实施例 1中的新型蚀刻液，装入喷雾机，调整蚀刻温度分别为 0 V , 室温， 35°C和 50°C，用高压 N₂挤压该新型蚀刻液通过喷淋头对上述掺 A1 的 ZnO基透明导电膜进行喷胶接触进行刻蚀。蚀刻后，用去离子水冲洗表面并吹干，保留光阻胶的情况下，用显微镜拍摄刻蚀后的图样。 Then, the novel etching solution of Example 1 was placed in a sprayer, and the etching temperatures were adjusted to 0 V, room temperature, 35 ° C, and 50 ° C, respectively. The new etching solution was pressed through a sprinkler head with high pressure N _{2 .} The above-mentioned A1-doped ZnO-based transparent conductive film is subjected to a glue contact for etching. After etching, the surface was rinsed with deionized water and dried, and in the case where the photoresist was left, the etched pattern was taken with a microscope.

发明人结合蚀刻图样分析 "新型蚀刻液作为 0基透明导电薄膜的湿法蚀刻物料，其蚀刻过程中有如下特征- 1 ) 先是主要纵向蚀刻正面接触的 Zn0，湿法蚀刻的各向同性的特点因新型蚀刻液表面张力大而横向侧蚀不显著； The inventors combined the etching pattern to analyze the "new etching liquid as a wet etching material for the 0-based transparent conductive film, and the etching process has the following characteristics - 1) Firstly, the main longitudinal etching of the front contact Zn0, the isotropic characteristics of the wet etching due to the large surface tension of the new etching liquid and the lateral side etching is not significant;

2 )随着纵向蚀刻完 ZnO基薄膜后，蚀刻转变为横向侧蚀为主，且侧蚀速率主要由新型蚀刻液的胶体状态、及大的表面张力决定，因而其蚀刻界面清晰； 2) After the ZnO-based thin film is longitudinally etched, the etching transitions to lateral lateral etching, and the side etching rate is mainly determined by the colloidal state of the new etching liquid and the large surface tension, so that the etching interface is clear;

3) 横向侧蚀一段距离后，由于新型蚀刻液的胶体状态、及大的表面张力，侧蚀过程随着渗透 H离子的浓度减弱，侧蚀速度逐渐减缓，并趋于稳定。 3) After the lateral side etching for a certain distance, due to the colloidal state of the new etching solution and the large surface tension, the side etching process decreases with the concentration of the permeating H ions, and the side etching rate gradually slows down and tends to be stable.

实施例 3 Example 3

通过本实施例对本发明的新型蚀刻液的应用进行说明。 The application of the novel etching solution of the present invention will be described by way of this embodiment.

本发明的新型蚀刻液的上述特点用在 "氧化物材料体系"制备的精半导体光电器件、太阳能电池、 TFT薄膜晶体管、半导体集成电路和透明电极上的刻蚀上是极为有用。 The above-described characteristics of the novel etching liquid of the present invention are extremely useful for etching on fine semiconductor photovoltaic devices, solar cells, TFT thin film transistors, semiconductor integrated circuits, and transparent electrodes prepared by "oxide material systems".

将新型蚀刻液应用于半导体光电器件中氧化物材料的刻蚀，器件应用中典型的有采用 Al、 Ga、 Zn、 In基氧化物薄膜材料，典型为 AZ0、 GZ0、 IZ0或者其组合成分，作为 LED、太阳能电池等光电器件的透明导电薄膜，或者显示领域 TFT等电子器件应用的透明电极，或者透明电子等领域的互联电极材料。这些器件领域都需要对精细电子部件中具有精细结构的氧化物材料的刻蚀，因此更需要刻蚀工艺中抑制侧蚀。 The new etching solution is applied to the etching of oxide materials in semiconductor optoelectronic devices. The device applications typically use Al, Ga, Zn, In-based oxide thin film materials, typically AZ0, GZ0, IZ0 or a combination thereof. A transparent conductive film of an optoelectronic device such as an LED or a solar cell, or a transparent electrode for use in an electronic device such as a TFT in the field of display, or an interconnect electrode material in the field of transparent electrons or the like. These device fields require etching of oxide structures having fine structures in fine electronic components, and thus it is more desirable to suppress side etching in the etching process.

将新型蚀刻液应用于显示用 TFT电子器件中氧化物材料的刻蚀， IGZO- TFT 中的 IGZ0氧化物膜包括 In-Ga- Zn- 0，且晶态下的该组成表示 InGa0₃ (ZnO) _n (m是小于 6的自然数)。透明 IGZ0氧化物膜是其中含有微晶并具有小于 10¹⁸/立方厘米的电子载流子浓度的透明非晶半导体氧化物膜。构成 IGZO- TFT主要器件结构有两类：顶栅极底接触型 TFT、底栅极顶接触型 TFT。 The novel etching solution is applied to the etching of the oxide material in the TFT electronic device for display. The IGZ0 oxide film in the IGZO-TFT includes In-Ga-Zn- 0, and the composition in the crystalline state represents InGa0 ₃ (ZnO). _n (m is a natural number less than 6). The transparent IGZ0 oxide film is a transparent amorphous semiconductor oxide film containing crystallites therein and having an electron carrier concentration of less than 10 ¹⁸ /cm 3 . There are two main types of main device structures for IGZO-TFT: top gate bottom contact type TFT and bottom gate top contact type TFT.

在蚀刻透明氧化物例如上述的 IGZ0、 IZ0和 IG0构成的 TFT器件时，由于 IGZ0、 IZ0和 IG0需要与 IT0构成堆叠结构，在只使用透明氧化物例如 IGZ0、 IZ0和 IG0 而不使用 ITO制备器件的情况下，这些氧化物的蚀刻选择性成为主要主题。如果蚀刻选择性不足，就会出现可能蚀刻不应被蚀刻的材料的情况，这可能增加电子器件性能的变动，因此造成收率降低。 In etching a transparent oxide such as the above-described TFT devices composed of IGZ0, IZ0, and IG0, since IGZ0, IZ0, and IG0 need to form a stacked structure with IT0, a device is prepared using only transparent oxides such as IGZ0, IZ0, and IG0 without using ITO. In the case of these oxides, the etching selectivity of these oxides has become a main theme. If the etching selectivity is insufficient, there is a case where it is possible to etch a material which should not be etched, which may increase variations in the performance of the electronic device, thus causing a decrease in yield.

本发明新型蚀刻液具有高的选择比，而且速率可控，刻蚀面平整，不会将刻蚀的图案带到下一层，新型蚀刻液能够提供含 In、 Ga和 Zn并且形成在衬底上的氧化物半导体膜的高选择性蚀刻液及方法，并且能够在衬底上形成具有稳定和均匀的电特性的半导体器件。工业实用性 The novel etching liquid of the invention has a high selection ratio, and the rate is controllable, the etching surface is flat, and the etching pattern is not brought to the next layer, and the novel etching liquid can provide In, Ga and Zn and is formed on the substrate. A highly selective etching liquid and method of the above oxide semiconductor film, and capable of forming a semiconductor device having stable and uniform electrical characteristics on the substrate. Industrial applicability

在工业应用上，也能够将使用透明氧化物膜作为有源层的 TFT施加到软塑料膜上，并且能够应用于柔性显示器的像素驱动器、识别用 IC卡、产品 ID标签等的领域。 In industrial applications, it is also possible to apply a TFT using a transparent oxide film as an active layer to a soft plastic. The film can be applied to the field of a pixel driver for a flexible display, an IC card for identification, a product ID tag, and the like.

将新型蚀刻液应用于氧化物材料构成的堆叠结构的刻蚀，如很多时候，我们并不需要完全把 AZO/GZO/ZnO薄膜蚀刻到底，而是需要更为精确地蚀刻到具体的某一层中，如需要将刻蚀图案精确定义到导电性能高的 GZ0 层。以 AZO/GZO/ZnO "三明治 "结构 ZnO为例，中间层 GZ0作为电流横向扩展层，具有很好的导电性，我们希望电极的引线可以与此层接触，这要求放慢蚀刻的速率，把蚀刻的时间拉长。本发明的新型蚀刻液溶液是一种很好的蚀刻剂。如醋酸的电离 H+离子浓度蚀刻 ZnO的速率缓慢，而由于其不完全电离的特性使得 H⁺离子浓度在一段时间内保持稳定，不受消耗影响，从而保持蚀刻速率不变。 The new etching solution is applied to the etching of a stacked structure composed of an oxide material. For example, many times, we do not need to completely etch the AZO/GZO/ZnO film to the end, but need to etch it to a specific layer more accurately. In the case, it is necessary to precisely define the etching pattern to the GZ0 layer with high conductivity. Taking AZO/GZO/ZnO "sandwich" structure ZnO as an example, the intermediate layer GZ0 acts as a laterally expanding layer of current and has good conductivity. We hope that the lead of the electrode can be in contact with this layer, which requires slowing the rate of etching. The etching time is elongated. The novel etching solution of the present invention is a good etchant. For example, the ionized H+ ion concentration of acetic acid etches ZnO at a slow rate, and due to its incomplete ionization characteristics, the H ⁺ ion concentration remains stable for a period of time without being affected by consumption, thereby keeping the etching rate constant.

将新型蚀刻液应用于采用 ZnO基氧化物材料构成的光电子器件中，比如由 ZnO/n- ZnO/i- ZnO/p- Zn0、 n- ZnO/n- Be。.₃Zn。.₇0/MQW/p- Be。.₃Zn。.₇0 /p-ZnO等堆叠结构构成的 ZnO基外延多层状结构的器件，这类堆叠由于蚀刻各层的成分相同，因此精确控制蚀刻深度、平整的刻蚀界面、抑制侧蚀等是这类器件刻蚀工艺的关键，而本发明中提出的将新型蚀刻液能解决这类结构或器件应用中的问题。 The novel etching solution is applied to an optoelectronic device composed of a ZnO-based oxide material, such as ZnO/n-ZnO/i-ZnO/p-Zn0, n-ZnO/n-Be. . ₃ Zn. . ₇ 0/MQW/p- Be. . ₃ Zn. ZnO-based epitaxial multilayer structure composed of stacked structures such as ₇ 0 /p-ZnO, such stacks have the same composition of etching layers, so precise control of etching depth, flat etching interface, suppression of side etching, etc. The key to the etching process of such devices, and the novel etching solution proposed in the present invention can solve the problems in the application of such structures or devices.

综上所述，但本发明并不局限于上述实施方式，本领域一般技术人员在本发明所揭露的技术范围内，可轻易想到的变化，均在本发明的保护范围之内。 In summary, the present invention is not limited to the above embodiments, and those skilled in the art can easily conceive changes within the scope of the present invention within the scope of the present invention.

序列表自由内容 Sequence table free content

Claims

权利要求书 claims

1、一种用于氧化物材料体系的新型蚀刻液，其特征在于：包括氧化物蚀刻溶液、起到稠度调节作用的调节剂以及水。 1. A new etching solution for oxide material systems, characterized by: including an oxide etching solution, a regulator that adjusts the consistency, and water.

2、如权利要求 1所述用于氧化物材料体系的新型蚀刻液，其特征在于：以重量计，所述新型蚀刻液中含有， 2. The new etching liquid for oxide material systems according to claim 1, characterized in that: by weight, the new etching liquid contains,

0. 01〜80wt %的氧化物蚀刻溶液； 0.01~80wt% oxide etching solution;

0. l〜80wt %的调节剂； 0.1~80wt% regulator;

余量的水。 remaining water.

3、如权利要求 1所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述氧化物材料体系为由锌、铟、镓、铝、锡、镉、铜、锶、钛金属元素构成的二元材料体系、三元材料体系、四元材料体系、多元材料体系、掺杂氧化物材料体系以及由上述材料体系中的两种或两种以上构成的复合材料体系，其中，所述二元材料体系的化学式可表示为 A_x0_y，其中 x>0、 y>0， A为上述各种金属元素中任意一种， 0为氧元素； 3. The novel etching solution for oxide material system according to claim 1, characterized in that: the oxide material system is composed of zinc, indium, gallium, aluminum, tin, cadmium, copper, strontium and titanium metal elements Binary material system, ternary material system, quaternary material system, multi-element material system, doped oxide material system and composite material system composed of two or more of the above material systems, wherein, the The chemical formula of the binary material system can be expressed as A _x 0 _y , where x>0, y>0, A is any one of the above various metal elements, and 0 is the oxygen element;

所述三元材料体系的化学式可表示为 Α_ΧΒΑ，其中 x〉0、 y〉0、 z〉0， A和 B分别为上述各种金属元素中任意一种， 0为氧元素； The chemical formula of the ternary material system can be expressed as A _X B A, where x>0, y>0, z>0, A and B are any one of the above various metal elements, and 0 is the oxygen element;

所述四元材料体系的化学式可表示为 A_xB_yC_z0_m, 其中 x〉0、 y>0、 z〉0、 m〉0， A、 B和 C分别为上述各种金属元素中任意一种， 0为氧元素； The chemical _formula _of the _quaternary material system can be expressed as _A Any one, 0 is oxygen element;

所述多元材料体系为含有四种以上上述提到的金属元素的氧化物；所述掺杂氧化物材料体系是在上述二元、三元、四元或多元材料体系中掺入第 III族元素或掺入第 IV族元素或渗入第七主族元素或掺入稀土元素或掺入 F—替代上述材料中 0²_。 The multi-element material system is an oxide containing more than four of the above-mentioned metal elements; the doped oxide material system is a Group III element doped in the above-mentioned binary, ternary, quaternary or multi-element material system. Or doped with Group IV elements, or doped with seventh main group elements, or doped with rare earth elements, or doped with F—replacing 0 ² _ in the above materials.

4、如权利要求 3所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述二元材料体系为氧化锌、氧化锡、氧化镓、氧化铟、氧化镉、氧化铝；所述三元材料体系为钛酸锶、锡酸镉、铟酸镉；所述四元材料体系为铟镓锌氧化合物；所述掺杂元素为第 III族元素中的硼、铝、镓、铟和锶，或第 IV族元素中的硅、锗、锡、铅、钛、镐和铪，或第七主族元素中的氟、氯，或掺入稀土元素中的锶、钇。 4. The novel etching solution for oxide material systems according to claim 3, characterized in that: the binary material system is zinc oxide, tin oxide, gallium oxide, indium oxide, cadmium oxide, and aluminum oxide; The ternary material system is strontium titanate, cadmium stannate, and cadmium indium oxide; the quaternary material system is indium gallium zinc oxide compound; the doping elements are boron, aluminum, gallium, indium and Strontium, or silicon, germanium, tin, lead, titanium, pickaxe and hafnium in Group IV elements, or fluorine and chlorine in Group VII elements, or strontium and yttrium doped in rare earth elements.

5、如权利要求 3所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述掺杂氧化物材料体系为 ZnO: In、 ZnO:Al、 ZnO:Ga、 ZnO:Sn、 ZnO:F、 ZnO:B、 Sn0₂: Sb、 Sn0₂:F、 Sn0₂:Al、 Sn0₂:Ga、 Sn0₂: ln、 In₂0₃:Sn、 In₂0₃:Al、 In₂0₃:Ga。 5. The novel etching solution for oxide material systems according to claim 3, characterized in that: The doped oxide material system is ZnO:In, ZnO:Al, ZnO:Ga, ZnO:Sn, ZnO:F, ZnO:B, _Sn02 :Sb, _Sn02 :F, _Sn02 :Al, _Sn02 : Ga, Sn0 ₂ : ln, In ₂ 0 ₃ : Sn, In ₂ 0 ₃ : Al, In ₂ 0 ₃ : Ga.

6、如权利要求 1所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述氧化物蚀刻溶液为无机酸溶液及其酸式盐溶液、有机酸溶液及其铵盐聚磺酸化合物和水碱溶液、碱溶液、盐溶液、双氧水溶液中任意一种，以及将上述氧化物蚀刻溶液任意混合而不会产生新的物质而构成的组合蚀刻液，以及异丙醇添加到磷酸溶液中形成的组合蚀刻液。 6. The novel etching solution for oxide material systems according to claim 1, characterized in that: the oxide etching solution is an inorganic acid solution and its acid salt solution, an organic acid solution and its ammonium salt polysulfonic acid Compounds and aqueous alkaline solutions, alkaline solutions, salt solutions, hydrogen peroxide solutions, and a combined etching solution in which the above-mentioned oxide etching solutions are arbitrarily mixed without generating new substances, and isopropyl alcohol is added to the phosphoric acid solution The combined etching solution formed in.

7、如权利要求 6所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述无机酸溶液为王水、硫酸、盐酸、硝酸、氢碘酸、高氯酸、磷酸、草酸、醋酸、碳酸、氢硫酸、硼酸中任意一种；所述有机酸溶液为有机羧酸化合物、乙酸、丙酸、丁酸、琥珀酸、柠檬酸、乳酸、苹果酸、酒石酸、丙二酸、马来酸、戊二酸、乌头酸、 1， 2， 3-丙烷三羧酸中任意一种；所述碱溶液为氨水；所述盐溶液为上述无机酸、有机酸和碱溶液反应后形成的各种盐溶液。 7. The novel etching solution for oxide material systems according to claim 6, characterized in that: the inorganic acid solution is aqua regia, sulfuric acid, hydrochloric acid, nitric acid, hydriodic acid, perchloric acid, phosphoric acid, oxalic acid, Any one of acetic acid, carbonic acid, hydrosulfuric acid, and boric acid; the organic acid solution is an organic carboxylic acid compound, acetic acid, propionic acid, butyric acid, succinic acid, citric acid, lactic acid, malic acid, tartaric acid, malonic acid, or horseradish Any one of lenic acid, glutaric acid, aconitic acid, and 1,2,3-propanetricarboxylic acid; the alkali solution is ammonia water; the salt solution is formed after the reaction of the above-mentioned inorganic acid, organic acid and alkali solution of various salt solutions.

8、如权利要求 6所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述氧化物蚀刻溶液为硫酸氨、硝酸氨、磷酸氨、氯化物弱酸盐、四甲基氢氧化铵、磷酸盐类化合物、草酸类化合物、氯化铁、氯化铵、三氯化铁。 8. The novel etching solution for oxide material systems according to claim 6, characterized in that: the oxide etching solution is ammonium sulfate, ammonium nitrate, ammonium phosphate, chloride weak acid salt, tetramethyl hydroxide Ammonium, phosphates, oxalates, ferric chloride, ammonium chloride, ferric chloride.

9、如权利要求 1所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述调节剂为聚乙二醇、甲氧基聚乙二醇、聚丙二醇、聚乙烯醇、胶体二氧化硅、羚甲基纤维素、羚甲基纤维素钠、水凝胶、海藻酸钠、液状石蜡、凡士林、植物油中一种或几种混合物。 9. The novel etching solution for oxide material systems according to claim 1, characterized in that: the regulator is polyethylene glycol, methoxypolyethylene glycol, polypropylene glycol, polyvinyl alcohol, colloidal dihydrogen One or several mixtures of silicon oxide, methyl cellulose, sodium methylcellulose, hydrogel, sodium alginate, liquid paraffin, petroleum jelly, vegetable oil.

10、如权利要求 1所述用于氧化物材料体系的新型蚀刻液，其特征在于- 所述水为去离子水。 10. The novel etching solution for oxide material systems according to claim 1, characterized in that - the water is deionized water.

11、如权利要求 1所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述新型蚀刻液的黏度值为 3〜50000 mPa S o 11. The new etching liquid for oxide material systems according to claim 1, characterized in that: the viscosity value of the new etching liquid is 3~50000 mPa So

12、如权利要求 1所述用于氧化物材料体系的新型蚀刻液，其特征在于：以重量计，所述新型蚀刻液中含有， 12. The new etching liquid for oxide material systems according to claim 1, characterized in that: by weight, the new etching liquid contains,

0. 01〜80^ %的磷酸或磷酸盐溶液； 0.01~80% phosphoric acid or phosphate solution;

0. l〜80wt %的聚乙二醇调节剂； 0.1~80wt% polyethylene glycol regulator;

余量的水。 remaining water.

13、如权利要求 12所述用于氧化物材料体系的新型蚀刻液，其特征在于：以重量计，所述新型蚀刻液中含有， 13. The new etching liquid for oxide material systems according to claim 12, characterized in that: by weight, the new etching liquid contains,

0. 01〜8(½1 %的磷酸或磷酸盐溶液； 0.01~8(½1% phosphoric acid or phosphate solution;

10〜90wt %的水。 10~90wt% water.

14、如权利要求 1〜13任意一项所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述新型蚀刻液还包括有添加剂，所述添加剂是表面活性剂、金属离子鳌合剂以及腐蚀抑制剂中一种或几种。 14. The new etching liquid for oxide material systems according to any one of claims 1 to 13, characterized in that: the new etching liquid also includes additives, and the additives are surfactants and metal ion chelating agents. and one or more corrosion inhibitors.

15、如权利要求 14所述用于氧化物材料体系的新型蚀刻液，其特征在于：所述添加剂的含量为 0. 0001wt %〜10wt %。 15. The new etching solution for oxide material systems as claimed in claim 14, characterized in that: the content of the additive is 0.0001wt%~10wt%.

16、如权利要求 1所述新型蚀刻液的蚀刻方法，其特征在于该方法包括如下步骤- 16. The etching method of the new etching liquid according to claim 1, characterized in that the method includes the following steps -

(1)在氧化物单层或多层材料体系上喷雾涂布光阻胶并去除部分光阻胶形成光阻胶图案； (1) Spray-coat photoresist on the oxide single-layer or multi-layer material system and remove part of the photoresist to form a photoresist pattern;

(2)将新型刻蚀液通过涂覆方式一次或多次涂覆在具有光阻胶图案的氧化物单层或多层上； (2) Coat the new etching solution once or multiple times on the oxide single or multiple layers with the photoresist pattern;

(3)利用新型刻蚀液蚀亥嗵过光阻胶图案选择性地蚀刻氧化物单层或多层。 (3) Use a new etching solution to etch through the photoresist pattern to selectively etch a single layer or multiple layers of oxide.

17、如权利要求 16所述新型蚀刻液的蚀刻方法，其特征在于：所述新型蚀刻液涂覆可以采用甩胶机、旋涂机、喷雾机来实现。 17. The etching method of the new etching liquid according to claim 16, characterized in that: the coating of the new etching liquid can be achieved by using a glue spinner, a spin coater, or a sprayer.

18、如权利要求 16所述新型蚀刻液的蚀刻方法，其特征在于：所述新型蚀刻液涂覆的厚度在 5〜10000腿。 18. The etching method of the new etching liquid according to claim 16, characterized in that: the thickness of the new etching liquid coating is between 5 and 10,000 μm.

19、如权利要求 16所述新型蚀刻液的蚀刻方法，其特征在于：所述新型蚀刻液涂覆的温度在 0〜200度。 19. The etching method of the new etching liquid according to claim 16, characterized in that: the coating temperature of the new etching liquid is between 0 and 200 degrees.

20、如权利要求 16所述新型蚀刻液的蚀刻方法，其特征在于：所述氧化物单层或多层材料体系为 ZnO材料体系，其蚀刻方法具体为：在沉积生长 ZnO基透明导电薄膜的衬底喷雾涂布光阻胶；进行曝光、显影，去除部分光阻胶，使得待刻蚀衬底暴露在外；对其进行烘烤；通过对待蚀刻衬底喷雾涂布上新型蚀刻液进行蚀刻；刻蚀时间为 0. 5分钟到 30分钟，蚀刻温度不高于 150摄氏度；去离子水冲洗；有机溶液去除光阻胶。 20. The etching method of the new etching liquid according to claim 16, characterized in that: the single-layer or multi-layer oxide material system is a ZnO material system, and the etching method is specifically: depositing and growing a ZnO-based transparent conductive film. The substrate is spray-coated with photoresist; exposed, developed, and part of the photoresist removed to expose the substrate to be etched; baked; etched by spray-coating a new etching liquid on the substrate to be etched; The etching time is 0.5 minutes to 30 minutes, the etching temperature is not higher than 150 degrees Celsius; rinse with deionized water; remove the photoresist with organic solution.

21、根据权利要求 20所述新型蚀刻液的蚀刻方法，其特征在于：所述 ZnO 基透明导电薄膜为 ZnO: Al、 ZnO:Ga、 ZnO: In, ZnO:Sn、 InGaZnO中任意一种或几种组合物。 21. The etching method of the new etching liquid according to claim 20, characterized in that: the ZnO-based transparent conductive film is any one or more of ZnO: Al, ZnO: Ga, ZnO: In, ZnO: Sn, and InGaZnO. kind of composition.

22、利用权利要求 1所述的新型蚀刻液在半导体光电器件、太阳能电池、 TFT薄膜晶体管、半导体集成电路、像素驱动器、识别用 IC卡、产品 ID标签和透明电极上氧化物材料体系中的刻蚀应用。 22. Utilize the new etching solution of claim 1 to engrave in semiconductor optoelectronic devices, solar cells, TFT thin film transistors, semiconductor integrated circuits, pixel drivers, identification IC cards, product ID labels and oxide material systems on transparent electrodes. Erosion application.