WO2023082462A1 - 氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法 - Google Patents

氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法 Download PDF

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WO2023082462A1
WO2023082462A1 PCT/CN2022/070660 CN2022070660W WO2023082462A1 WO 2023082462 A1 WO2023082462 A1 WO 2023082462A1 CN 2022070660 W CN2022070660 W CN 2022070660W WO 2023082462 A1 WO2023082462 A1 WO 2023082462A1
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etching
etching solution
nitride film
ammonium ions
regeneration
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PCT/CN2022/070660
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English (en)
French (fr)
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吴祥
李卫民
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中国科学院上海微系统与信息技术研究所
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Publication of WO2023082462A1 publication Critical patent/WO2023082462A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/02—Treatment of water, waste water, or sewage by heating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3105—After-treatment
    • H01L21/311—Etching the insulating layers by chemical or physical means
    • H01L21/31105—Etching inorganic layers
    • H01L21/31111—Etching inorganic layers by chemical means
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/16—Nitrogen compounds, e.g. ammonia

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  • the invention relates to the technical field of wet etching, in particular to a method for regenerating a nitride thin film etchant and an etching method for a nitride thin film.
  • nitride films such as silicon nitride films
  • silicon nitride films are often used as masking layers due to their excellent physical and chemical properties to prevent impurities such as sodium and water molecules from harming semiconductor devices. They are also often used as sacrificial films. When used Once complete, it is often removed using wet etching.
  • phosphoric acid mainly plays a catalytic role, and the consumption is small, and the main material component that reacts with silicon nitride is water.
  • the concentration of ammonium radical-containing compounds one of the etching products of silicon nitride in the phosphoric acid etching solution, increases.
  • the nitrogen element in the silicon nitride combines with the hydrogen element provided by the reactant in the etching solution to form an ammonium ion, and combines with another anion to form an ammonium-containing compound.
  • ammonium compounds usually dissociate into ammonium ions and anions in solution.
  • the concentration of ammonium ions continues to rise, resulting in the gradual ammonium salification of the etching solution, which cannot be used further, resulting in waste of the etching solution.
  • the existing method can only be regenerated by heating, but the ammonium-containing compound exists in the form of ammonium ions in strong acids, and direct heating cannot make it evaporate into ammonia molecules.
  • the inventor of the present application proposed an improvement scheme after long-term research.
  • the object of the present invention is to provide a kind of regeneration method of nitride thin film etchant and the etching method of nitride thin film, to solve the prior art, in carrying out nitrogen such as silicon nitride
  • nitrogen such as silicon nitride
  • the present invention can remove ammonium ions online without stopping the etching process, can increase the service life of the etching solution, reduce the operation of replacing the etching solution, improve production efficiency and reduce the etching cost.
  • the present invention provides a method for regeneration of nitride thin film etching solution, the regeneration method comprises the etching product ammonium radical in the etching solution produced after wet etching of nitride thin film Ions are removed to realize the step of etching solution regeneration.
  • the method for removing ammonium ions includes several of the following methods:
  • the solid adsorbent used to adsorb and remove ammonium ions added to the used etching solution includes cation exchange resin, molecular sieve, zirconia, silicon oxide, chelating polymer, surface-modified perfluoropolymer Several kinds of materials, polypropylene and polyethersulfone.
  • the nitride film includes several kinds of silicon nitride film, titanium nitride film, aluminum nitride film and gallium nitride film.
  • the etching solution includes several kinds of phosphoric acid, hydrofluoric acid and nitric acid.
  • the present invention also provides a method for etching a nitride film, which includes the step of wet etching the nitride film and wet etching the nitride film by using the regeneration method described in any of the above schemes.
  • the ammonium ion of the etching product in the etching solution generated after etching is removed to realize the step of regenerating the etching solution.
  • the used etchant is continuously regenerated online during the wet etching process of the nitride film.
  • the regeneration method of nitride thin film etching solution and the etching method of nitride thin film of the present invention have the following beneficial effects: the present invention can use the online method without stopping the etching process through the improved process. Removing ammonium ions can increase the service life of the etching solution, reduce the operation of replacing the etching solution, improve production efficiency and reduce etching costs, and reduce environmental pollution by reducing the discharge of waste liquid.
  • FIG. 1 shows an exemplary structural diagram of a wet etching device for performing the etching method of a nitride thin film provided by the present invention.
  • Embodiments of the present invention are described below through specific examples, and those skilled in the art can easily understand other advantages and effects of the present invention from the content disclosed in this specification.
  • the present invention can also be implemented or applied through other different specific implementation modes, and various modifications or changes can be made to the details in this specification based on different viewpoints and applications without departing from the spirit of the present invention.
  • the cross-sectional view showing the device structure will not be partially enlarged according to the general scale, and the schematic diagram is only an example, which should not limit the protection scope of the present invention.
  • the three-dimensional space dimensions of length, width and depth should be included in actual production.
  • spatial relation terms such as “below”, “below”, “below”, “below”, “above”, “on” etc. may be used herein to describe an element or element shown in the drawings.
  • a layer is referred to as being “between” two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present.
  • structures described as having a first feature "on top of" a second feature may include embodiments where the first and second features are formed in direct contact, as well as additional features formed between the first and second features. Embodiments between the second feature such that the first and second features may not be in direct contact.
  • the present invention provides a method for regenerating a nitride thin film etching solution.
  • the regeneration method includes etching in the etching solution (that is, the used etching solution) produced after the nitride thin film is wet etched.
  • the product ammonium ion is removed to realize the step of etching solution regeneration.
  • one of the wet etching products of nitride films such as silicon nitride is a compound containing ammonium radicals, which are dissociated into ammonium radical ions and anions in the etching solution. As the process continues, the concentration of ammonium ions continues to rise.
  • the present invention can improve the service life of the etching solution, reduce the operation of replacing the etching solution, improve production efficiency and reduce the etching cost by timely removing the ammonium ion in the etching product in the used etching solution. .
  • the method for removing ammonium ions in the used etching solution includes several of the following methods:
  • the method for removing ammonium ions in the used etching solution can be any one of the above methods, or two or more of the above methods can be used.
  • Add solid adsorbent to the liquid to absorb and remove ammonium ions for preliminary treatment then add water to the etching solution obtained after preliminary treatment, heat and evaporate to further remove residual ammonium ions, and then supplement with low-concentration ammonium ions ions (preferably completely free of ammonium ion etching solution, but in fact the concentration of ammonium ion in the etching solution is difficult to be zero, and can only be as close to zero as possible) fresh etching solution to reduce The concentration of ammonium ions in the final etching solution.
  • the above methods can also be combined in other ways, which is not strictly limited.
  • the solid adsorbent used to adsorb and remove ammonium ions added to the etching solution after use includes but is not limited to cation exchange resins, molecular sieves, zirconia, silicon oxide, chelating polymers, surface modified Several kinds of perfluoropolymers, polypropylene and polyethersulfone, that is, the solid adsorbent can be one kind, or two or more kinds.
  • deionized water is preferably added.
  • the nitride film includes but not limited to several kinds of silicon nitride film, titanium nitride film, aluminum nitride film and gallium nitride film, and the etching solution includes several kinds of phosphoric acid, hydrofluoric acid and nitric acid. kind.
  • the type of etchant usually depends on the type of the nitride film. For example, if the nitride film is a silicon nitride film, the etchant may be a phosphoric acid etchant.
  • the etching residual liquid generated by etching is synchronously regenerated to timely remove the ammonium ions contained in the etching residual liquid, and the regenerated etching liquid is continuously transported to the etching residual liquid.
  • the etching operation continues in the etching equipment.
  • the regeneration process of the etching solution can also be separated from the etching operation, that is, the etching residue generated by the etching can be collected in a centralized manner, and after unified regeneration treatment, it can be uniformly transported to the etching equipment to process the nitride film on the substrate. etch.
  • the present invention also provides a method for etching a nitride film, which includes the step of wet etching the nitride film and wet etching the nitride film by the regeneration method described in any of the above schemes.
  • the ammonium ion of the etching product in the etching residual liquid generated after etching is removed to realize the step of etching liquid regeneration.
  • the used etching solution is continuously regenerated online, that is, the etching solution is continuously circulated without interrupting the etching process. Regeneration (but regeneration operations are usually started later than etch operations).
  • the etching method of the nitride thin film of the present invention can be, for example, phosphoric acid wet etching of silicon nitride, and certainly can also be the etching of titanium nitride, aluminum nitride or other nitride thin films, and the etchant can also be For nitric acid, hydrofluoric acid or a mixture of acids.
  • FIG. 1 is a schematic structural diagram of an exemplary wet etching device for performing the etching method for a nitride thin film provided by the present invention. As shown in Figure 1.
  • the wet etching equipment includes an etching tank 1 and an ammonium ion removal module 3, and the etching tank 1 and the ammonium ion removal module 3 are connected through pipelines.
  • the substrate to be etched such as a wafer with a silicon nitride film formed on its surface
  • the resulting etching residue that is, the used etching liquid
  • the ion removal module 3 wherein the ammonium ion of the etching product is removed by the ammonium ion removal module 3, so that the regeneration of the etching solution can be realized.
  • the etching tank 1 can be a monolithic etching tank, or a batch-type processing tank. When it is a batch-type processing tank, the etching tank 1 can be an overflow tank, that is, it includes both an inner tank and a batch-type processing tank. In the outer tank, the substrate is wet-etched in the inner tank, and the resulting etching residue overflows into the outer tank, flows into the pipeline through the drain port of the outer tank and flows through the ammonium ion removal module, and after regeneration treatment It can be transported back to the inner tank to form a circulation loop.
  • the wet etching equipment may also include one or more of a pump 2, a filter 4, a heater 5, and a monitoring module 6, and these modules are preferably set at the same time, and these modules are all connected to pipelines Pass.
  • the pump 2 can be arranged between the etching tank 1 and the ammonium ion removal module 3, so that the etching residue discharged in the etching tank 1 is transported to the ammonium ion removal module 3 by the power provided by the pump, and filtered
  • the device 4 can be set between the liquid outlet of the ammonium ion removal module 3 and the heater to further remove impurity particles in the etching solution
  • the heater 5 is set between the filter 4 and the liquid inlet of the etching tank 1 In between, the temperature of the regenerated etching solution is adjusted so that the regenerated etching solution meets the requirements of the etching process.
  • the monitoring module 6 can be single or more than two, such as wherein one is arranged between the pump 2 and the ammonium ion removal module 3, and one is arranged between the ammonium ion removal module 3 and the filter 4, which can effectively monitor the ammonium ion Changes in the ion concentration, so as to realize the monitoring of the working effect of the ammonium ion removal module. For example, if it is monitored that the concentration of ammonium ions contained in the etching solution does not change before and after the ammonium ion removal module, it may be that the ammonium ion removal module is malfunctioning or that its processing is caused by too much ammonium ion removal. If the capacity decreases, the ammonium ion removal module can be cleaned or replaced directly.
  • the ammonium ion removal module can be single or multiple. When there are multiple ammonium ion removal modules, the multiple ammonium ion removal modules can be connected in series or in parallel, or partly in parallel or partly in series. There is no strict limitation on this. Adopting the etching method provided by the invention helps to improve etching efficiency and reduce etching cost.
  • the present invention provides a method for regenerating a nitride thin film etching solution and a method for etching a nitride thin film.
  • the regeneration method includes the step of removing the ammonium ions of the etching product in the etching residual liquid produced after the wet etching of the nitride thin film, so as to realize the regeneration of the etching liquid.
  • the present invention can remove ammonium ions online without stopping the etching process, thereby improving the service life of the etching solution, reducing the operation of replacing the etching solution, improving production efficiency and reducing etching costs ,
  • environmental pollution can be reduced by reducing the discharge of waste liquid. Therefore, the present invention effectively overcomes various shortcomings in the prior art and has high industrial application value.

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Abstract

本发明提供一种氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法。所述再生方法包括将氮化物薄膜湿法刻蚀后产生的刻蚀残液中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。本发明通过改善的工艺，可在不停止刻蚀工艺的情况下，在线去除铵根离子，可提高刻蚀液的使用寿命，减少更换刻蚀液的操作，提高生产效率和降低刻蚀成本，同时通过降低废液的排放可以减少环境污染。

Description

氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法 技术领域
本发明涉及湿法刻蚀技术领域，特别是涉及一种氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法。
背景技术
在半导体制造中，氮化物薄膜，例如氮化硅薄膜因具备优异的物理化学性质，常作为掩蔽层使用，用以避免钠及水分子等杂质危害半导体器件，也经常作为牺牲膜使用，当使用完成之后，经常使用湿法蚀刻的方法去除。
以氮化硅薄膜的湿法刻蚀为例，氮化硅在磷酸中刻蚀发生的化学反应方程式如下：
3Si 3N 4+4H 3PO 4+36H 2O＝4(NH 4) 3PO 4+9Si(OH) 4
在刻蚀液中，磷酸主要起催化的作用，消耗量较少，与氮化硅反应的主要的物质成分为水。随着氮化硅刻蚀反应的进行，磷酸刻蚀液中氮化硅的刻蚀产物之一的含铵根的化合物浓度上升。氮化硅中的氮元素与刻蚀液中的反应物提供的氢元素结合形成铵根离子，与另一阴离子结合成为含铵根的化合物。根据铵根离子的特性，铵根化合物在溶液中通常解离为铵根离子与阴离子。随着刻蚀工艺的持续进行，铵根离子的浓度持续上升，导致刻蚀液逐渐铵盐化，无法继续使用，造成刻蚀液的浪费。
现有的方法只有加热再生，但含铵根的化合物在强酸中以铵根离子形式存在，直接加热无法使其形成氨气分子蒸发。对此，本申请的发明人经长期研究，提出了一种改善方案。
发明内容
鉴于以上所述现有技术的缺点，本发明的目的在于提供一种氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法，以解决现有技术中，在进行氮化硅等氮化物薄膜的湿法刻蚀工艺中，通过加热液体等方法难以有效去除刻蚀液中的刻蚀产物铵根化合物，无法实现刻蚀液的循环利用而只能频繁更换刻蚀液，导致刻蚀液使用寿命短、用量大，造成生产成本增加、生产效率低下以及带来环境污染等问题。本发明通过改善的工艺，可在不停止刻蚀工艺的情况下，在线去除铵根离子，可提高刻蚀液的使用寿命，减少更换刻蚀液的操作，提高生产效率和降低刻蚀成本。
为实现上述目的及其他相关目的，本发明提供一种氮化物薄膜刻蚀液的再生方法，所述再生方法包括将氮化物薄膜湿法刻蚀后产生的刻蚀液中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。
可选地，去除铵根离子的方法包括如下方法中的若干种：
1)于使用后的刻蚀液中加入固体吸附剂吸附去除铵根离子；
2)于使用后的刻蚀液中加入水后加热去除铵根离子；
3)于使用后的刻蚀液中加入含低浓度的铵根离子的新鲜刻蚀液替换部分使用后的含高浓度的铵根离子的刻蚀液。
可选地，于使用后的刻蚀液中加入的用于吸附去除铵根离子的固体吸附剂包括阳离子交换树脂、分子筛、氧化锆、氧化硅、螯合聚合物、表面改性的全氟聚合物、聚丙烯及聚醚砜中的若干种。
可选地，所述氮化物薄膜包括氮化硅薄膜、氮化钛薄膜、氮化铝薄膜和氮化镓薄膜中的若干种。
可选地，所述刻蚀液包括磷酸、氢氟酸和硝酸中的若干种。
本发明还提供一种氮化物薄膜的刻蚀方法，所述刻蚀方法包括对氮化物薄膜进行湿法刻蚀的步骤以及采用如上述任一方案中所述的再生方法将氮化物薄膜湿法刻蚀后产生的刻蚀液中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。
可选地，对氮化物薄膜进行湿法刻蚀的过程中持续对使用后的刻蚀液进行在线再生。
如上所述，本发明的氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法，具有以下有益效果：本发明通过改善的工艺，可在不停止刻蚀工艺的情况下，通过在线去除铵根离子，可提高刻蚀液的使用寿命，减少更换刻蚀液的操作，提高生产效率和降低刻蚀成本，同时通过降低废液的排放可以减少环境污染。
附图说明
图1显示为执行本发明提供的氮化物薄膜的刻蚀方法的湿法刻蚀设备的一例示性结构示意图。
元件标号说明
1                      刻蚀槽
2                      泵
3                      铵根离子去除模块
4                      过滤器
5                      加热器
6                      监测模块
具体实施方式
以下通过特定的具体实例说明本发明的实施方式，本领域技术人员可由本说明书所揭露的内容轻易地了解本发明的其他优点与功效。本发明还可以通过另外不同的具体实施方式加以实施或应用，本说明书中的各项细节也可以基于不同观点与应用，在没有背离本发明的精神下进行各种修饰或改变。如在详述本发明实施例时，为便于说明，表示器件结构的剖面图会不依一般比例作局部放大，而且所述示意图只是示例，其在此不应限制本发明保护的范围。此外，在实际制作中应包含长度、宽度及深度的三维空间尺寸。
为了方便描述，此处可能使用诸如“之下”、“下方”、“低于”、“下面”、“上方”、“上”等的空间关系词语来描述附图中所示的一个元件或特征与其他元件或特征的关系。将理解到，这些空间关系词语意图包含使用中或操作中的器件的、除了附图中描绘的方向之外的其他方向。此外，当一层被称为在两层“之间”时，它可以是所述两层之间仅有的层，或者也可以存在一个或多个介于其间的层。
在本申请的上下文中，所描述的第一特征在第二特征“之上”的结构可以包括第一和第二特征形成为直接接触的实施例，也可以包括另外的特征形成在第一和第二特征之间的实施例，这样第一和第二特征可能不是直接接触。
需要说明的是,本实施例中所提供的图示仅以示意方式说明本发明的基本构想，遂图式中仅显示与本发明中有关的组件而非按照实际实施时的组件数目、形状及尺寸绘制，其实际实施时各组件的型态、数量及比例可为一种随意的改变，且其组件布局型态也可能更为复杂。为使图示尽量简洁，各附图中并未对所有的结构全部标示。
现有技术中在去除氮化物薄膜刻蚀后的刻蚀液中的铵根离子的方法只有加热去除，但含铵根的化合物在强酸中以铵根离子形式存在，加热无法使其形成氨气分子蒸发，难以真正实现刻蚀液再生。对此，本申请的发明人经长期研究，提出了一种改善方案。
具体地，本发明提供一种氮化物薄膜刻蚀液的再生方法，所述再生方法包括将氮化物薄膜湿法刻蚀后产生的刻蚀液(即使用后的刻蚀液)中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。具体地，像氮化硅等氮化物薄膜的湿法刻蚀产物之一是含铵根的化合物，含铵根的化合物在刻蚀液中解离为铵根离子与阴离子，随着刻蚀工艺的持续进行，铵根离子的浓度持续上升，如果不及时去除，会导致刻蚀液逐渐铵盐化，无法继续使用，造成刻蚀液的浪费。而本发明则通过将使用后的刻蚀液中的刻蚀产物中的铵根离子及时去除，可提高刻 蚀液的使用寿命，减少更换刻蚀液的操作，提高生产效率和降低刻蚀成本。
在较佳的示例中，去除使用后的刻蚀液中的铵根离子的方法包括如下方法中的若干种：
1)于使用后的刻蚀液中加入固体吸附剂吸附去除铵根离子；
2)于使用后的刻蚀液中加入水后加热去除铵根离子；
3)于使用后的刻蚀液中加入含低浓度的铵根离子的刻蚀液替换部分使用后的含高浓度的铵根离子的刻蚀液(补充的刻蚀液中的铵根离子的浓度小于使用后的刻蚀液中的铵根离子的浓度)。
即去除使用后的刻蚀液中的铵根离子的方法，可采用上述方法中的任意一种，也可以采用上述方法中的两种或两种以上，比如可以先于使用后的刻蚀残液中加入固体吸附剂吸附去除铵根离子以进行初步处理，然后对初步处理后得到的刻蚀液加入水后加热蒸发，以进一步去除残余的铵根离子，之后再补充含低浓度的铵根离子(较佳地为完全不含铵根离子的刻蚀液，但实际上刻蚀液中的铵根离子浓度很难为零，只能尽量做到趋近于零)的新鲜刻蚀液以降低最终的刻蚀液中的铵根离子的浓度。当然，在其他示例中，也可以将上述方法以其他方式组合，对此不做严格限制。
在一示例中，于使用后的刻蚀液中加入的用于吸附去除铵根离子的固体吸附剂包括但不限于阳离子交换树脂、分子筛、氧化锆、氧化硅、螯合聚合物、表面改性的全氟聚合物、聚丙烯及聚醚砜中的若干种，即固体吸附剂可以为一种，也可以为两种或两种以上。
在一示例中，于使用后的刻蚀液中加水并通过加热去除铵根离子的过程中，较佳地为加入去离子水。
所述氮化物薄膜包括但不限于氮化硅薄膜、氮化钛薄膜、氮化铝薄膜和氮化镓薄膜中的若干种，而所述刻蚀液包括磷酸、氢氟酸和硝酸中的若干种。刻蚀液的类型通常依据氮化物薄膜的类型而定，比如所述氮化物薄膜为氮化硅薄膜，则刻蚀液可以为磷酸刻蚀液。
本发明提供的再生方法，通过在刻蚀过程中同步对刻蚀产生的刻蚀残液进行再生处理以及时去除刻蚀残液中含有的铵根离子，再生后的刻蚀液持续输送至刻蚀设备中继续进行刻蚀作业。刻蚀液的再生过程也可以脱离于刻蚀作业，即，可以将刻蚀产生的刻蚀残液集中收集，经统一进行再生处理后再统一输送至刻蚀设备中对基板的氮化物薄膜进行刻蚀。
本发明还提供一种氮化物薄膜的刻蚀方法，所述刻蚀方法包括对氮化物薄膜进行湿法刻蚀的步骤以及采用上述任一方案中所述的再生方法将氮化物薄膜湿法刻蚀后产生的刻蚀残液中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。且在较佳的示例中，对氮化物薄膜进行湿法刻蚀的过程中持续对使用后的刻蚀液进行在线再生，即在刻蚀工艺不中断的情 况下，持续进行刻蚀液的循环再生(但再生作业的开启通常晚于刻蚀作业)。本发明的氮化物薄膜的刻蚀方法例如可以为氮化硅的磷酸湿法刻蚀，当然还可以为氮化钛、氮化铝或其他氮化物薄膜的刻蚀，而刻蚀液则还可以为硝酸、氢氟酸或多种酸的混合。图1为执行本发明提供的氮化物薄膜的刻蚀方法的湿法刻蚀设备的一示例性结构示意图。如图1所示。该湿法刻蚀设备包括刻蚀槽1和铵根离子去除模块3，刻蚀槽1和铵根离子去除模块3通过管路相连通。待刻蚀的基板，例如表面形成有氮化硅薄膜的晶圆放置于该刻蚀槽1中进行刻蚀后，产生的刻蚀残液(即使用后的刻蚀液)经管路流入铵根离子去除模块3，其中的刻蚀产物铵根离子被铵根离子去除模块3去除，由此可实现刻蚀液的再生。所述刻蚀槽1可以为单片式刻蚀槽，也可以为批次型处理槽，当为批次型处理槽时，该刻蚀槽1可以为溢流槽，即同时包括内槽和外槽，基板在内槽内进行湿法刻蚀，产生的刻蚀残液溢流至外槽中，经外槽的排液口流入管路并流经铵根离子去除模块，经再生处理后可以重新输送至内槽中而形成一循环回路。在进一步的示例中，所述湿法刻蚀设备还可以包括泵2、过滤器4、加热器5和监测模块6中的一个或多个，优选同时设置这些模块，这些模块均与管路相连通。例如，泵2可以设于刻蚀槽1和铵根离子去除模块3之间，以通过泵提供的动力将刻蚀槽1中排放的刻蚀残液输送至铵根离子去除模块3中，过滤器4可以设置于铵根离子去除模块3的出液口和加热器之间，以进一步去除刻蚀液中的杂质颗粒，加热器5则设置于过滤器4与刻蚀槽1的进液口之间，以对再生后的刻蚀液进行温度调节，以使再生后的刻蚀液符合刻蚀工艺要求。而监测模块6可以为单个或两个以上，比如其中一个设置于泵2和铵根离子去除模块3之间，一个设置于铵根离子去除模块3和过滤器4之间，可以有效监测铵根离子浓度的变化，从而实现对铵根离子去除模块的工作效果监测。比如，若监测到刻蚀液流经铵根离子去除模块前后，其中含有的铵根离子浓度基本没变化，则可能是铵根离子去除模块出现故障或因吸附的铵根离子过多导致其处理能力下降，此时可以对铵根离子去除模块进行清洗或直接更换。铵根离子去除模块可以为单个或多个，当为多个时，多个铵根离子去除模块可以为串联或并联，或部分并联，部分串联，对此不做严格限制。采用本发明提供的刻蚀方法，有助于提供刻蚀效率和降低刻蚀成本。
综上所述，本发明提供一种氮化物薄膜刻蚀液的再生方法和氮化物薄膜的刻蚀方法。所述再生方法包括将氮化物薄膜湿法刻蚀后产生的刻蚀残液中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。本发明通过改善的工艺，可在不停止刻蚀工艺的情况下，通过在线去除铵根离子，可提高刻蚀液的使用寿命，减少更换刻蚀液的操作，提高生产效率和降低刻蚀成本，同时通过降低废液的排放可以减少环境污染。所以，本发明有效克服了现有技术 中的种种缺点而具高度产业利用价值。
上述实施例仅例示性说明本发明的原理及其功效，而非用于限制本发明。任何熟悉此技术的人士皆可在不违背本发明的精神及范畴下，对上述实施例进行修饰或改变。因此，举凡所属技术领域中具有通常知识者在未脱离本发明所揭示的精神与技术思想下所完成的一切等效修饰或改变，仍应由本发明的权利要求所涵盖。

Claims (7)

  1. 一种氮化物薄膜刻蚀液的再生方法，其特征在于，所述再生方法包括将氮化物薄膜湿法刻蚀后产生的刻蚀液中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。
  2. 根据权利要求1所述的再生方法，其特征在于，去除铵根离子的方法包括如下方法中的若干种：
    1)于使用后的刻蚀液中加入固体吸附剂吸附去除铵根离子；
    2)于使用后的刻蚀液中加入水后加热去除铵根离子；
    3)于使用后的刻蚀液中加入含低浓度的铵根离子的新鲜刻蚀液替换部分使用后的含高浓度的铵根离子的刻蚀液。
  3. 根据权利要求2所述的再生方法，其特征在于，于使用后的刻蚀液中加入的用于吸附去除铵根离子的固体吸附剂包括阳离子交换树脂、分子筛、氧化锆、氧化硅、螯合聚合物、表面改性的全氟聚合物、改性的聚丙烯及改性的聚醚砜中的若干种。
  4. 根据权利要求1所述的再生方法，其特征在于，所述氮化物薄膜包括氮化硅薄膜、氮化钛薄膜、氮化铝薄膜和氮化镓薄膜中的若干种。
  5. 根据权利要求1所述的再生方法，其特征在于，所述刻蚀液包括磷酸、氢氟酸和硝酸中的若干种。
  6. 一种氮化物薄膜的刻蚀方法，其特征在于，所述刻蚀方法包括对氮化物薄膜进行湿法刻蚀的步骤以及采用如权利要求1-5任一项所述的再生方法将氮化物薄膜湿法刻蚀后产生的刻蚀液中的刻蚀产物铵根离子进行去除，以实现刻蚀液再生的步骤。
  7. 根据权利要求6所述的刻蚀方法，其特征在于，对氮化物薄膜进行湿法刻蚀的过程中持续对使用后的刻蚀液进行在线再生。
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